Catalyst component and catalyst containing the component for polymerization of olefins

ABSTRACT

The present invention relates to a metallocene compound as a catalyst component for the polymerization of olefins, said compound, is stable to air and moisture so that generates no hydrogen halide by hydrolysis and easily handled, and has a high storage stability and a high catalyst activity. Specifically, the catalyst component for the polymerization of olefins comprises a transition metal composition represented by the general formula [1] and [2]: 
     
       
         (R a  Cp) m (R′ b  Cp)M(—X—Ar—Y c ) 4−(m+n)   [1] 
       
     
     
       
         R″(R d  Cp) (R′ e  Cp)M(—X—Ar—Y c ) 2   [2] 
       
     
     wherein M is Ti, Zr or Hf; (R a  Cp),(R′ b  Cp), (R d  Cp) and (R″ e  Cp ) each is a radical having the cyclopentadienyl skeleton; R″ is a radical which links (R d  Cp) and (R′ e  Cp); (—X—Ar—Y c ) is a grouping in which the aromatic ring Ar substituted by a specified radical Y bonds to M through an oxygen or sulphur atom X.

This application is a divisional of U.S. application Ser. No. 09/220,589filed on Dec. 28, 1998, which is a continuation on part ofPCT/JP97/04441 filed on Dec. 4, 1997.

TECHNICAL FIELD

The present invention relates to a catalyst component for thepolymerization of olefins, a polymerization catalyst containing thecomponent and a process for the polymerization of olefins by using thecatalyst, and more particularly, to a catalyst component for thepolymerization of olefins which is stable to air, moisture and so on andnot corrosive to metal, a polymerization catalyst containing saidcomponent, having a high polymerization activity and being capable ofproducing olefin polymers, and a process for the polymerization ofolefins.

BACKGROUND ART

Recently, as a catalyst which can homopolymerize ethylene orcopolymerize ethylene and α-olefin with a high polymerization activity,there is proposed a new catalyst for the polymerization of olefinscomprising a transition metal compound such as metallocene compound ofzirconium and an organic aluminum oxy compound. As a process for thehomo- or copolymerization of ethylene by using such catalyst, there hasbeen proposed, for example, in Japanese Patent Application Laid-openNos. Sho 58(1983)-19309, Sho 60(1985)-35007, etc.

In such a prior art, it has been disclosed that as a transition metalcompound component, a metallocene compound is available, which has analkadienyl radical such as a cyclopentadienyl radical, etc, as a ligandfor the transition metal, and further an alkyl radical, a halogen atom,etc.

However, the metallocene compound in such prior arts may show a highpolymerization activity as a compound having a halogen atom bounddirectly to the transition metal atom, but need a treatment with alcoholor water after the polymerization depending on the kind of olefins andthe process for the polymerization, so that hydrogen halide may beformed disadvantageously which may occur rusts and corrosions inequipments. Further, a metallocene compound having an alkyl radicalbound directly to the metal atom has high polymerization activityrelatively and does not form. undesirable hydrogen halide, but there aresome disadvantages that it is extremely unstable to a little air ormoisture, is apt to lower the catalyst activity remarkably bydeterioration in the operation or to deteriorate with time in storage,as a result, a special care and equipment to the handling and storage ofcatalyst component are required. Thus, for example, as seen in JapanesePatent Application Laid-open No. Sho 62(1987)-230802, there has beenproposed a process in which the halogen atom or alkyl radical bound tothe metal atom is converted to an alkoxy or phenoxy radical to eliminatethe formation of hydrogen halide and improve the stability of themetallocene compound. In this case, however, disadvantageously theactivity as catalyst for the polymerization of olefins is in generallowered.

Accordingly, it has been strongly desired to develop as a metallocenecompound, a transition metal compound, which satisfies at the same timethree requirements that it does not contain a halogen atom directlybound to the metal atom, as a result, it does not generate undesirablehydrogen halide, that it is stable to air and moisture so that it may bedealt with easily and has a high storage stability and that it has ahigh activity on using as a catalyst for the polymerization of olefins.And also it has been strongly desired to provide a process for thepolymerization of olefins therewith.

After studying earnestly in view of the present status as mentionedabove,: it has been found that a metallocene compound may eliminate thedisadvantages as mentioned above which has a radical comprising acyclopentadienyl skeleton coordinated to the transition metal and inwhich an aromatic ring substituted with a special substituent is boundthrough an oxygen or a sulphur to the transition metal, and it shows anexcellent activity on using it as a catalyst for the polymerization ofolefins resulting in the accomplishment of the present invention.

DISCLOSURE OF INVENTION

Accordingly, the present invention relates at first to a catalystcomponent for the polymerization of olefins which comprises a transitionmetal compound represented by the general formula [1] or [2]:

(R_(a) CP)_(m)(R′_(b) Cp)_(n)M (—X—Ar—Y_(c))_(4−(m+n))  [1]

wherein M represents titanium, zirconium or hafnium, Cp represents aradical having the cyclopentadienyl skeleton, R and R′ represent ahydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkylor an alkylsilyl radical, X represents an oxygen or a sulphur atom, Arrepresents an aromatic ring, Y represents a hydrogen atom, a hydrocarbonradical, a silyl radical, a halogen atom, a halogenated hydrocarbonradical, a nitrogen-containing organic radical, an oxygen-containingorganic radical or a sulphur-containing organic radical, each of a and bis an integer of 0 to 5, each of m and n is an integer of 0 to 3 andthat m+n is an integer of 1 to 3, and c is an integer of 1 to 5, provisoY does not represent a hydrogen atom when Ar is a benzene ring;

R″(R_(d) Cp) (R′_(e) Cp) M(—X—Ar—Y_(c))₂  [2]

wherein M represents titanium, zirconium or hafnium, Cp represents aradical having the cyclopentadienyl skeleton, R and R′ represent ahydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkylor an alkylsilyl radical, R″ represents a divalent radical which links(R_(d) Cp) and (R′_(e) Cp) and is selected from an alkylene, anarylalkylene, a dialkylsilylene, a dialkylgermylene, analkylphosphindiyl or an alkylimino radical, X represents an oxygen or asulphur atom, Ar represents an aromatic radical, Y represents a hydrogenatom, a hydrocarbon radical, a silyl radical, a halogen atom, ahalogenated hydrocarbon radical, a nitrogen-containing organic radical,an oxygen-containing organic radical or a sulphur-containing organicradical, d and e each represents an integer of 0 to 4, and c is aninteger of 1 to 5, proviso that Y is not a hydrogen atom when Ar is abenzene ring.

Secondly, the present invention relates to a catalyst for thepolymerization of olefins comprising [A] a transition metal compoundrepresented by the above-mentioned general formula [1] or [2], [B] anorganic aluminum oxy compound or a cation generator and occasionally [C]an organic aluminum compound, and thirdly to a: process for thepolymerization of olefins characterized by polymerizing orcopolymerizing olefins in the presence of said catalyst for thepolymerization of olefins.

The metallocene compound as a catalyst component for the polymerizationof olefins has as mentioned-above in general a halogen atom or an alkylradical as the groupings to bond the transition metal and thepolymerization activity thereof is remarkably lowered when all groupingsare converted to a phenoxy or thiophenoxy radical. However, the presentinventors have found unexpected function in which in case a specifiedsubstutient is introduced to an aromatic: ring like a phenoxy radical orthiophenoxy radical or the like, a higher polymerization activity isrealized without the reduction of activity rather than the metallocenecompound to which a halogen atom or an alkyl radical is bound.

The present invention will be illustrated in detail hereinafter, inwhich the term “polymerizations ” means the homopolymerization andcopolymerization.

The metallocene catalyst component according to the present invention isa transition metal compound represented by any one of the following twogeneral formulae:

(R_(a) CP)_(m)(R′_(b) Cp)_(n)M(—X—Ar—Y_(c))_(4−(m+n))  [1]

wherein M represents titanium, zirconium or hafnium, Cp represents aradical having the cyclopentadienyl skeleton, R and R′ represent ahydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkylor an alkylsilyl radical, X represents an oxygen or a sulphur atom, Arrepresents an aromatic ring, Y represents a hydrogen atom, a hydrocarbonradical, a silyl radical, a halogen atom, a halogenated hydrocarbonradical, a nitrogen-containing organic radical, an oxygen-containingorganic radical or a sulphur-containing radical, each of a and b is aninteger of 0 to 5, each of m and n is an integer of 0 to 3 and m+n is aninteger of 1 to 3, and c is an integer of 1-5, proviso that Y is not ahydrogen atom when Ar is a benzene ring;

R″(R_(d) Cp)(R′_(c) Cp) M (—X—Ar—Y_(c))₂  [2]

wherein M represents titanium, zirconium or hafnium, Cp represents aradical having the cyclopentadienyl skeleton, R and R′ represent ahydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkylor an alkylsilyl radical, R″ represents a divalent radical which links(R_(d) Cp) and (R′_(e) Cp) and is selected from an alkylene, anarylalkylene, a dialkylsilylene, a dialkylgermylene, analkylphosphindiyl, or an alkylimino radical, X represents an oxygen or asulphur atom, Ar represents an aromatic ring, Y represents a hydrogenatom, a hydrocarbon radical, a silyl radical, a halogen atom, ahalogenated hydrocarbon radical, a nitrogen-containing organic radical,an oxygen-containing organic radical or a sulphur-containing organicradical, each of d and e is an integer of 0 to 4, and c is an integer of1 to 5, proviso that Y is not a hydrogen atom when Ar is a benzene ring.

In the general formulae [1] and [2], the ligand Cp is not critical butmay be a grouping having the cyclopentadienyl skeleton and include notonly a cyclopentadienyl radical but the cyclopentadienyl radicals inwhich two vicinal carbon atoms in the cyclopentadienyl ring bond toother carbon atoms to form a 4- or 5- or 6-membered ring. As thecyclopentadienyl radicals in which two vicinal carbon atoms in thecyclopentadienyl ring bond to other carbon atoms to form a 4- or 5- or6-membered ring, there are mentioned, for example, an indenyl,tetrahydroindenyl, fluorenyl radical, etc.

In the general formulae [1] and [2], R and R′ each is preferably, ahydrogen, an alkyl radical having 1 to 20 carbon atoms, an alkenylradical having 2-20 carbon atoms, an aryl radical having 6 to 20 carbonatoms, an alkylaryl radical having 7 to 20 carbon atoms, an arylalkylradical having 7 to 20 carbon atoms or an alkylsilyl radical having 3 to20 carbon atoms.

In the general formula [1], as the grouping (R_(a) Cp) and (R′_(b) Cp)having the cyclopentadienyl skeleton, for example, cyclopentadienyl,methylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl,isopropylcyclopentadienyl, n-butylcyclopentadienyl,isobutylcyclopentadienyl, tert-butylcyclopentadienyl,1,2-dimethylcyclopentadienyl, 1,3-dimethylcyclopentadienyl,1,2,4-trimethylcyclopentadienyl, 1,2,3-trimethylcyclopentadienyl,tetramethylcyclopentadienyl, pentamethylcyclopentadienyl,trimethylsilylcyclopentadienyl,trimethylsilyltetramethylcyclopentadienyl,(phenyldimethylsilyl)cyclopentadienyl, triphenylsilylcyclopentadienyl,1,3-di(trimethylsilyl)cyclopentadienyl, cyclohexylcyclopentadienyl,allylcyclopentadienyl, benzylcyclopentadienyl, phenylcyclopentadienyl,tolylcyclopentadienyl, indenyl, 1-methylindenyl, 2-methylindenyl,2,4-dimethylindenyl, 4,7-dimethoxyindenyl, 4,7-dichloroindenyl,5,6-dimethylindenyl, 2-methyl-4-ethyl-indenyl,2-methyl-4,6-diisopropyl-indenyl, naphthylindenyl,4,5,6,7-tetrahydroindenyl, 2-methyl-tetrahydroindenyl, fluorenyl,2,7-di-tert-butylfluorenyl.

In the general formula [2], R″ represents a divalent radical having 1 to20 carbon atoms, which links (R_(d) Cp) and (R′_(e) Cp), and there arementioned concretely alkylene, such as methylene, ethylene; alkylidene,such as ethylidene, propylidene, isopropylidene; arylalkylidene, such asphenylmethylidene, diphenylmethylidene; silylene, such asdimethylsilylene, diethylsilylene, dipropylsilylene,diisopropylsilylene, methylethylsilylene, methylisopropylsilylene,methyltert-butylsilylene, methylphenylsilylene, diphenylsilylene;germylene, such as dimethylgermylene, diethylgermylene,dipropylgermylene, diisopropylgermylene, diphenylgermylene,methylethylgermylene, methylisopropylgermylene,methyltert-butylgermylene, methylphenylgermylene, diphenylgermylene;alkylphophinediyl, such as methylphosphinediyl; alkylimino, such asmethylimino; alkylboranediyl, such as methylborandiyl.

And, as the grouping R″ (R_(d) Cp) and (R′_(e) Cp) having thecyclopentadienyl skeleton in the general formula [2], there arementioned, for example, ethylenebisindenyl, diphenylmethylenebisindenyl,dimethylsilylenebisindenyl, isopropylidenebisindenyl,dimethylsilylenebistetrahydroindenyl,isopropylidenecyclopentadienyl-1-fluorenyl,diphenylmethylencyclopentadienyl-1-fluorenyl,dimethylsilylenecyclopentadienyl-1-fluorenyl, dimethylsilylenbis(2,3,5-trimethylcyclopentadienyl),dimethylsilylenebis(2,4-dimethylcyclopentadienyl),dimethylsilylenebis(3-methylcyclopentadienyl),isopropylidenecyclopentadienyl-methylcyclopentadienyl,isopropylidenecyclopentadienyl-2,3,5-trimethylcyclopentadienyl,diphenylmethylenecyclopentadienyl-methylcyclopentadienyl,diphenylmethylenecyclopentadienyl-2,4-dimethylcyclopentadienyl,diphenylmethylenecyclopentadienyl-2,3,5-trimethylcyclopentadienyl,dimethylsilylencyclopentadienyl-methylcyclopentadienyl,dimethylsilylenecyclopentadienyl-2,4-dimethylcyclopentadienyl,dimethylsilylenecyclopentadienyl-2,3,5-trimethylcyclopentadienyl,isopropylidene-2,4-dimethylcycropentadienyl-1-fluorenyl,diphenylmethylene-2,4-dimethylcyclopentadienyl-1-fluorenyl,dimethylsilylene-2,4-dimethylcyclopentadienyl-1-fluorenyl,cyclohexylidenecyclopentadienyl-1-fluorenyl,dimethylgermylenebis-1-indenyl.

In the general formulae [1] and [2], Ph represents an aromatic radical,such as, for example, a benzene, naphthalene, anthrathene, indenyl, andphenanthrene ring.

Further, in the general formulae [1] and [2], the substituent Y is aradical which is selected from the group of a hydrogen atom, ahydrocarbon radical, a silyl radical, a halogen atom, a halogenatedhydrocarbon radical, a nitrogen-containing organic radical, anoxygen-containing organic radical or a sulphur-containing organicradical. And more concretely, it is a hydrocarbon radical such as analkyl having 1-10 carbon atoms, an aryl having 6-10 carbon atoms, analkenyl having 2-10 carbon atoms, an alkynyl having 2-10 carbon atoms,an arylalkyl having 7-20 carbon atoms, an arylalkenyl having 8-20 carbonatoms and an alkylaryl having 7-20 carbon atoms, or a silyl radical suchas an alkylsilyl, an arylsilyl and the like, wherein the alkyl radicalmay include various kind of geometric isomers including cycloalkyl,proviso that as mentioned above a hydrogen atom is excluded when Ph is abenzene ring.

When the substituent Y is a hydrocarbon atom, there are mentioned analkyl radical having 1-10 carbon atoms such as, for example, methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,cyclohexyl, cyclooctyl, norbornyl; an aryl radical having 6-10 carbonatoms such as, for example, phenyl, naphthyl; an alkenylradical having2-10 carbon atoms such as, for example, vinyl, propenyl; an alkynylradical having 2-10 carbon atoms such as, for example, ethynyl,propynyl; an arylalkyl radical having 7-20 carbon atoms such as, forexample, benzyl, phenethyl; an arylalkenyl radical having 8-20 carbonatoms such as, for example, stylyl, cinnamyl; and an alkylaryl radicalhaving 7-20 carbon atoms such as, for example, tolyl, xylyl, mesyl,respectively.

When the substituent Y is an alkylsilyl radical, there are mentionedconcretely, for example, trimethylsilyl and triethylsilyl radical, andwhen the substituent Y is an arylsilyl radical, there are mentioned adiphenylmethylsilyl and triphenylsilyl radical.

When the substutient Y is a halogen atom, there are mentionedconcretely, for example, a fluorine, chlorine, bromine, iodine atom, andwhen the substutient Y is a halogenated hydrocarbon radical, there arementioned concretely, for example, chloromethyl, fluoromethyl,bromomethyl, iodomethyl, dichloromethyl, difluoromethyl, dibromomethyl,diiodomethyl, trichloromethyl, trifluoromethyl, chlorodifluoromethyl,2,2,2-trifluoroethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl,chlorophenyl, fluorophenyl, bromophenyl, iodophenyl, perfluorophenyl,chlorotetrafluorophenyl radical.

When the substutient Y is a nitrogen-containing organic radical, thereare mentioned concretely, for example, a cyano, nitro, nitroso,isocyanide, cyanate, isocyanate, N-methylamino, anilino,N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino,N,N-diphenylamino, formamide, acetamide, N-methylacetamide,N-phenylacetamide radical.

When the substutient Y is an oxygen-containing organic radical, thereare mentioned concretely, for example, a methoxy, ethoxy, propoxy,butoxy, phenoxy, formyl, acetyl, propyonyl, butylyl, valeryl, pyvaloyl,acyloyl, benzoyl, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl,acetoxy, benzoyloxy radical.

When the substutient Y is an sulphur-containing organic radical, thereare mentioned concretely, for example, a methylthio, ethylthio,phenylthio, methylsulfinyl, ethylsulfinyl, benzenesulfiniyl,trisulfinyl, tolylsulfinyl, mesyl, tosyl radical.

The symbol of c in the general formulae [1] and [2] is a value which isselected from 1 to 5. In case c is 2 to 5 and the plural substutient Yare bonded together, the same and/or different substutient areavailable.

As the transition metal compounds according to the definition of thegeneral formula [1] mentioned above, the following compounds may beexemplified: dicyclopentadienylbis(2-fluorophenoxy)zirconium,dicyclopentadienylbis(3-fluorophenoxy)zirconium,dicyclopentadienylbis(4-fluorophenoxy)zirconium,dicyclopentadienylbis(2-chlorophenoxy)zirconium,dicyclopentadienylbis(3-chlorophenoxy)zirconium,dicyclopentadienylbis(4-chlorophenoxy)zirconium,dicyclopentadienylbis(2-bromophenoxy)zirconium,dicyclopentadienylbis(3-bromophenoxy)zirconium,dicyclopentadienylbis(4-bromophenoxy)zirconium,dicyclopentadienylbis(2-iodophenoxy)zirconium,dicyclopentadienylbis(3-iodophenoxy)zirconium,dicyclopentadienylbis(4-iodophenoxy)zirconium,dicyclopentadienylbis(2,3-difluorophenoxy)zirconium,dicyclopentadienylbis(2,4-difluorophenoxy)zirconium,dicyclopentadienylbis(2 5-difluorophenoxy)zirconium,dicyclopentadienylbis(2,6-difluorophenoxy)zirconium,dicyclopentadienylbis(3,4-difluorophenoxy)zirconium,dicyclopentadienylbis(3,5-difluorophenoxy)zirconium,dicyclopentadienylbis(2,3-dichlorophenoxy)zirconium,dicyclopentadienylbis(2,4-dichlorophenoxy)zirconium,dicyclopentadienylbis(2,5-dichlorophenoxy)zirconium,dicyclopentadienylbis(2,6-dichlorophenoxy)zirconium,dicyclopentadienylbis(3,4-dichlorophenoxy)zirconium,dicyclopentadienylbis(3,5-dichlorophenoxy)zirconium,dicyclopentadienylbis(2,3,4-trifluorophenoxy)zirconium,dicyclopentadienylbis(2,3,5-trifluorophenoxy)zirconium,dicyclopentadienylbis(2,3,6-trifluorophenoxy)zirconium,dicyclopentadienylbis(2,4,5-trifluorophenoxy)zirconium,dicyclopentadienylbis(2,4,6-trifluorophenoxy)zirconium,dicyclopentadienylbis(3,4,5-trifluorophenoxy)zirconium,dicyclopentadienylbis(2,3,5,6-tetrafluorophenoxy)zirconium,dicyclopentadienylbis(pentafluorophenoxy)zirconium,dicyclopentadienylbis(2-fluoromethylphenoxy)zirconium,dicyclopentadienylbis(3-fluoromethylphenoxy)zirconium,dicyclopentadienylbis(4-fluoromethylphenoxy)zirconium,dicyclopentadienylbis(2-chloromethylphenoxy)zirconium,dicyclopentadienylbis(3-chloromethylphenoxy)zirconium,dicyclopentadienylbis(4-chloromethylphenoxy)zirconium,dicyclopentadienylbis(2-trifluoromethylphenoxy)zirconium,dicyclopentadienylbis(3-trifluoromethylphenoxy)zirconium,dicyclopentadienylbis,(4-trifluoromethylhenoxy)zirconium,dicyclopentadienylbis(3,5-di-trifluoromethyl)phenoxy)zirconium,dicyclopentadienylbis(2-(2,2,2-trifluoroethyl)phenoxy)zirconium,dicyclopentadienylbis(3-(2,2,2-trifluoroethyl)phenoxy)zirconium,dicyclopentadienylbis(4-(2,2,2-trifluoroethyl)phenoxy)zirconium,dicyclopentadienylbis(2-trichloromethylphenoxy)zirconium,dicyclopentadienylbis(3-trichloromethylphenoxy)zirconium,dicyclopentadienylbis(4-methylphenoxy)zirconiumdicyclopentadienylbis(2-methylphenoxy)zirconium,dicyclopentadienylbis(3-methylphenoxy)zirconium,dicyclopentadienylbis(4-methylphenoxy)zirconium,dicyclopentadienylbis(2,3dimethylphenoxy)zirconium,dicyclopentadienylbis(2,4-dimethylphenoxy)zirconium,dicyclopentadienylbis(2,5-dimethylphenoxy)zirconium,dicyclopentadienylbis(2,4-dimethylphenoxy)zirconium,dicyclopentadienylbis(3,4-dimethylphenoxy)zirconium,dicyclopentadienylbis(3,5-dimethylphenoxy)zirconium,dicyclopentadienylbis(2,3,4-trimethylphenoxy)zirconium,dicyclopentadienylbis(2,3,5-trimethylphenoxy)zirconium,dicyclopentadienylbis(2,3,6-trimethylphenoxy)zirconium,dicyclopentadienylbis(2,4,5-trimethylphenoxy)zirconium,dicyclopentadienylbis(2,4,6-trimethylphenoxy)zirconium,dicyclopentadienylbis(3,4,5-trimethylphenoxy)zirconium,dicyclopentadienylbis(pentamethylphenoxy)zirconium,dicyclopentadienylbis(2-methyl-4-fluorophenoxy)zirconium,dicyclopentadienylbis(2-chloro-4-fluorophenoxy)zirconium,dicyclopentadienylbis(2-chloro-4-trifluoromethylphenoxy)zirconium,dicyclopentadienylbis(2-fluoro-4-trifluoromethylphenoxy)zirconium,dicyclopentadienylbis(2-trifluoromethyl-4-florophenoxy)zirconium,dicyclopentadienylbis(2-ethylphenoxy)zirconium,dicyclopentadienylbis(3-ethylphenoxy)zirconium,dicyclopentadienylbis(4-ethylphenoxy)zirconium,dicyclopentadienylbis(2-isopropylphenoxy)zirconium,dicyclopentadienylbis(3-isopropylphenoxy)zirconium,dicyclopentadienylbis(4-isopropylphenoxy)zirconium,dicyclopentadienylbis(2-tert-butylphenoxy)zirconium,dicyclopentadienylbis(3-tert-butylphenoxy)zirconium,dicyclopentadienylbis(4-tert-butylphenoxy)zirconium,dicyclopentadienylbis(3,5-di-tert-butylphenoxy)zirconium,dicyclopentadienylbis(2-trimethylsilylphenoxy)zirconium,dicyclopentadienylbis(3-trimethylsilylphenoxy)zirconium,dicyclopentadienylbis(4-trimethylsilylphenoxy)zirconium,dicyclopentadienylbis(2-cyclohexylphenoxy)zirconium,dicyclopentadienylbis(3-cyclohexylphenoxy)zirconium,dicyclopentadienylbis(4-cyclohexylphenoxy)zirconium,dicyclopentadienylbis(1-naphthyloxy)zirconium,dicyclopentadienylbis(2-naphthyloxy)zirconium,dicyclopentadienylbis(8-trifluoromethy-1-naphthyloxy)zirconium,dicyclopentadienylbis(2,8-dimethyl-1-naphthyloxy)zirconium,dicyclopentadienylbis(1-tert-butyl-2-naphthyloxy)zirconium,dicyclopentadienylbis(8-bromo-2-naphthyloxy)zirconium,dicyclopentadienylbis(2-phenylphenoxy)zirconium,dicyclopentadienylbis(3-phenylphenoxy)zirconium,dicyclopentadienylbis(4-phenylphenoxy)zirconium,dicyclopentadienylbis(2-benzylphenoxy)zirconium,dicyclopentadienylbis(3-benzylphenoxy)zirconium,dicyclopentadienylbis(4-benzylphenoxy)zirconium,dicyclopentadienylbis(2-tolylphenoxy)zirconium,dicyclopentadienylbis(3-tolylphenoxy)zirconium,dicyclopentadienylbis(4-tolylphenoxy)zirconium,dicyclopentadienylbis(2-vinylphenoxy)zirconium,dicyclopentadienylbis(3-vinylphenoxy)zirconium,dicyclopentadienylbis(4-vinylphenoxy)zirconium,dicyclopentadienylbis(2-(2-propenyl)phenoxy)zirconium,dicyclopentadienylbis(3-(2-propenyl)phenoxy)zirconium,dicyclopentadienylbis(4-(2-propenyl)phenoxy)zirconium,dicyclopentadienylbis(2-methyl-6-(2-propenyl)phenoxy)zirconium,dicyclopentadienylbis(2-ethynylphenoxy)zirconium,dicyclopentadienylbis(3-ethynylphenoxy)zirconium,dicyclopentadienylbis(4-ethynylphenoxy)zirconium,dicyclopentadienylbis(2-methoxyphenoxy)zirconium,dicyclopentadienylbis(3-methoxyphenoxy)zirconium,dicyclopentadienylbis(4-methoxyphenoxy)zirconium,dicyclopentadienylbis(2-tert-butoxyphenoxy)zirconium,dicyclopentadienylbis(3-tert-butoxyphenoxy)zirconium,dicyclopentadienylbis(4-tert-butoxyphenoxy)zirconium,dicyclopentadienylbis(2-phenoxyphenoxy)zirconium,dicyclopentadienylbis(3-phenoxyphenoxy)zirconium,dicyclopentadienylbis(4-phenoxyphenoxy)zirconium,dicyclopentadienylbis(2-formylphenoxy)zirconium,dicyclopentadienylbis(3-formylphenoxy)zirconium,dicyclopentadienylbis(4-formylpwhenoxy)zirconium,dicyclopentadienylbis(2-acetylphenoxy)zirconium,dicyclopentadienylbis(3-acetylphenoxy)zirconium,dicyclopentadienylbis(4-acetylphenoxy)zirconium,dicyclopentadienylbis(2-benzoylphenoxy)zirconium,dicyclopentadienylbis(3-benzoylphenoxy)zirconium,dicyclopentadienylbis(4-benzoylphenoxy)zirconium,dicyclopentadienylbis(2-methoxycarbonylphenoxy)zirconium,dicyclopentadienylbis(3-methoxycarbonylphenoxy)zirconium,dicyclopentadienylbis(4-methoxycarbonylphenoxy)zirconium,dicyclopentadienylbis(2-aetoxyphenoxy)zirconium,dicyclopentadienylbis(3-acetoxyphenoxy)zirconum,dicyclopentadienylbis(4-acetoxyphenoxy)zirconium,dicyclopentadienylbis(2-cyanophenoxy)zirconium,dicyclopentadienylbis(3-cyanophenoxy)zirconium,dicyclopentadienylbis(4-cyanophenoxy)zirconium,dicyclopentadienylbis(2-nitrophenoxy)zirconium,dicyclopentadienylbis(3-nitrophenoxy)zirconium,dicyclopentadienylbis(4-nitrophenoxy)zirconium,dicyclopentadienylbis(2-anilinophenoxy)zirconium,dicyclopentadienylbis(3-anilinophenoxy)zirconium,dicyclopentadienylbis(4-anilinophenoxy)zirconium,dicyclopentadienylbis(2-dimethylaminophenoxy)zirconium,dicyclopentadienylbis(3-dimethylaminophenoxy)zirconium,dicyclopentadienylbis(4-dimethylaminophenoxy)zirconium,dicyclopentadienylbis(2-dimethylaminomethylphenoxy)zirconium,dicyclopentadienylbis(3-dimethylaminomethylphenoxy)zirconium,dicyclopentadienylbis(4-dimethylaminomethylphenoxy)zirconium,dicyclopentadienylbis(2-formylaminophenoxy)zirconium,dicyclopentadienylbis(3-formylaminophenoxy)zirconium,dicyclopentadienylbis(4-formylaminophenoxy)zirconium,dicyclopentadienylbis(2-acetylaminophenoxy)zirconium,dicyclopentadienylbis(3-acetylaminophenoxy)zirconium,dicyclopentadienylbis(4-acetylaminophenoxy)zirconium,dicyclopentadienylbis(2-thiomethoxyphenoxy)zirconium,dicyclopentadienylbis(3-thiomethoxyphenoxy)zirconium,dicyclopentadienylbis(4-thiomethoxyphenoxy)zirconium,dicyclopentadienylbis(2-thiophenoxyphenoxy)zirconium,dicyclopentadienylbis(3-thiophenoxyphenoxy)zirconium,dicyclopentadienylbis(4-thiophenoxyphenoxy)zirconium,dicyclopentadienylbis(2-methylsulfinylphenoxy)zirconium,dicyclopentadienylbis(3-methylsulfinylphenoxy)zirconium,dicyclopentadienylbis(4-methylsulfinylphenoxy)zirconium,dicyclopentadienylbis(2-mesylphenoxy)zirconium,dicyclopentadienylbis(3-mesylphenoxy)zirconium,dicyclopentadienylbis(4-mesylphenoxy)zirconium,dicyclopentadienylbis(2-tosylphenoxy)zirconium,dicyclopentadienylbis(3-tosylphenoxy)zirconium,dicyclopentadienylbis(4-tosylphenoxy)zirconium,dicyclopentadienylbis(2-trifluoromethanesulfonylphenoxy)zirconium,dicyclopentadienylbis(3-trifluoromethanesulfonylphenoxy)zirconium,dicyclopentadienylbis(4-trifluoromethanesulfonylphenoxy)zirconium,dicyclopentadienylbis(2-methylthiophenoxy)zirconium,dicyclopentadienylbis(3-methylthiophenoxy)zirconium,dicyclopentadienylbis(4-methylthiophenoxy)zirconium,dicyclopentadienylbis(2-tert-butylthiophenoxy)zirconium,dicyclopentadienylbis(3-tert-butylthiophenoxy)zirconium,dicyclopentadienylbis(4-tert-butylthiophenoxy)zirconium,dicyclopentadienylbis(2-fluorothiophenoxy)zirconium,dicyclopentadienylbis(3-fluorothiophenoxy)zirconium,dicyclopentadienylbis(4-fluorothiophenoxy)zirconium,dicyclopentadienylbis(2-chlorothiophenoxy)zirconium,dicyclopentadienylbis(3-chlorothiophenoxy)zirconium,dicyclopentadienylbis(4-chlorothiophenoxy)zirconium,dicyclopentadienylbis(2-trifluoromethylthiophenoxy)zirconium,dicyclopentadienylbis(3-trifluoromethylthiophenoxy)zirconium,dicyclopentadienylbis(4-trifluoromethylthiophenoxy)zirconium,dicyclopentadienylbis(2-methoxythiophenoxy)zirconium,dicyclopentadienylbis(3-methoxythiophenoxy)zirconium,dicyclopentadienylbis(4-methoxythiophenoxy)zirconium,bis(methylcyclopentadienyl)bis(2-chlorophenoxy)zirconium,bis(methylcyclopentadienyl)bis(3-chlorophenoxy)zirconium,bis(methylcyclopentadienyl)bis(4-chlorophenoxy)zirconium,bis(methylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium,bis(methylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium,bis(methylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,bis(methylcyclopentadienyl)bis(2-phenylphenoxy)zirconium,bis(methylcyclopentadienyl)bis(3-phenylphenoxy)zirconium,bis(methylcyclopentadienyl)bis(4-phenylphenoxy)zirconium,bis(1,2-dimethylcyclopentadienyl)bis(2-ethylphenoxy)zirconium,bis(1,2-dimethylcyclopentadienyl)bis(3-ethylphenoxy)zirconium,bis(1,2-dimethylcyclopentadienyl)bis(4-ethylphenoxy)zirconium,bis(1,2-dimethylcyclopentadienyl)bis(2,4-diethylphenoxy)zirconium,bis(1,2-dimethylcyclopentadienyl)bis(2,5-diethylphenoxy)zirconium,bis(1,2-dimethylcyclopentadienyl)bis(2-cyanophenoxy)zirconium,bis(1,2-dimethylcyclopentadienyl)bis(3-cyanophenoxy)zirconium,bis(1,2-dimethylcyclopentadienyl)bis(4-cyanophenoxy)zirconium,bis(1,2-dimethylcyclopentadienyl)bis(2-bromophenoxy)zirconium,bis(1,2-dimethylcyclopentadienyl)bis(3-bromophenoxy)zirconium,bis(1,2-dimethylcyclopentadienyl)bis(4-bromophenoxy)zirconium,bis(1,3-dimethylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium,bis(1,3-dimethylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium,bis(1,3-dimethylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,bis(1,3-dimethylcyclopentadienyl)bis(2-tert-butylphenoxy)zirconium,bis(1,3-dimethylcyclopentadienyl)bis(3-tert-butylphenoxy)zirconium,bis(1,3-dimethylcyclopentadienyl)bis(4-tert-butylphenoxy)zirconium,bis(1,3-dimethylcyclopentadienyl)bis(2-chlorophenoxy)zirconium,bis(1,3-dimethylcyclopentadienyl)bis(3-chlorophenoxy)zirconium,bis(1,3-dimethylcyclopentadienyl)bis(4-chlorophenoxy)zirconium,bis(1,2,3-trimethylcyclopentadienyl)bis(2-fluorophenoxy)zirconium,bis(1,2,3-trimethylcyclopentadienyl)bis(3-fluorophenoxy)zirconium,bis(1,2,3-trimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,bis(1,2,3-trimethylcyclopentadienyl)bis(2-isopropylphenoxy)zirconium,bis(1,2,3-trimethylcyclopentadienyl)bis(3-isopropylphenoxy)zirconium,bis(1,2,3-trimethylcyclopentadienyl)bis(4-isopropylphenoxy)zirconium,bis(1,2,3-trimethylcyclopentadienyl)bis(2-nitrophenoxy)zirconium,bis(1,2,3-trimethylcyclopentadienyl)bis(3-nitrophenoxy)zirconium,bis(1,2,3-trimethylcyclopentadienyl)bis(4-nitrophenoxy)zirconium,bis(1,2,4-trimethylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium,bis(1,2,4-trimethylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium,bis(1,2,4-trimethylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,bis(1,2,4-trimethylcyclopentadienyl)bis(2-methylphenoxy)zirconium,bis(1,2,4-trimethylcyclopentadienyl)bis(3-methylphenoxy)zirconium,bis(1,2,4-trimethylcyclopentadienyl)bis(4-methylphenoxy)zirconium,bis(1,2,4-trimethylcyclopentadienyl)bis(2,4-dimethylphenoxy)zirconium,bis(1,2,4-trimethylcyclopentadienyl)bis(2,4-dichlorophenoxy)zeirconium,bis(1,2,4-trimethylcyclopentadienyl)bis(2-tert-butylphenoxy)zirconium,bis(1,2,4-trimethylcyclopentadienyl)bis(3-tert-butylphenoxy)zirconium,bis(1,2,4-trimethylcyclopentadienyl)bis(4-tert-butylphenoxy)zirconium,bis(1,2,3,4-tetramethylcyclopentadienyl)bis(2-methoxyphenoxy)zirconium,bis(1,2,3,4-tetramethylcyclopentadienyl)bis(3-methoxyphenoxy)zirconium,bis(1,2,3,4-tetramethylcyclopentadienyl)bis(4-methoxyphenoxy)zirconium,bis(1,2,3,4-tetramethylcyclopentadienyl)bis(2-iodophenoxy)zirconium,bis(1,2,3,4-tetramethylcyclopentadienyl)bis(3-iodophenoxy)zirconium,bis(1,2,3,4-tetramethylcyclopentadienyl)bis(4-iodophenoxy)zirconium,bis(1,2,3,4-tetramethylcyclopentadienyl)bis(2-thiomethylphenoxy)zirconium,bis(1,2,3,4-tetramethylcyclopentadienyl)bis(3-thiomethylphenoxy)zirconium,bis(1,2,3,4-tetramethylcyclopentadienyl)bis(4-thiomethylphenoxy)zirconium,bis(pentamethylcyclopentadienyl)bis(2-fluorophenoxy)zirconium,bis(pentamethylcyclopentadienyl)bis(3-fluorophenoxy)zirconium,bis(pentamethhylcycllpentadienyl)bis(4-fluorophenoxy)zirconium,bis(ethylcyclopentadienyl)bis(2-ethylphenoxy)zirconium,bis(ethylcyclopentadienyl)bis(3-ethylphenoxy)zirconium,bis(ethylcyclopentadienyl)bis(4-ethylphenoxy)zirconium,bis(isopropylcyclopentadienyl)bis(2-acetylphenoxy)zirconium,bis(isopropylcyclopentadienyl)bis(3-acetylphenoxy)zirconium,bis(isopropylcyclopentadienyl)bis(4-acetylphenoxy)zirconium,bis(isopropylcyclopentadienyl)bis(2-methylphenoxy)zirconium,bis(isopropylcyclopentadienyl)bis(3-methylphenoxy)zirconium,bis(isopropylcyclopentadienyl)bis(4-methylphenoxy)zirconium,bis(n-butylcyclopentadienyl)bis(2-chlorophenoxy)zirconium,bis(n-butylcyclopentadienyl)bis(3-chlorophenoxy)zirconium,bis(n-butylcyclopentadienyl)bis(4-chlorophenoxy)zirconium,bis(n-butylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium,bis(n-butylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium,bis(n-butylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,bis(n-butylcyclopentadienyl)bis(2-tert-butylphenoxy)zirconium,bis(n-butylcyclopentadienyl)bis(3-tert-butylphenoxy)zirconium,bis(n-butylcyclopentadienyl)bis(4-tert-butylphenoxy)zirconium,bis(n-butylcyclopentadienyl)bis(2-cyanophenoxy)zirconium,bis(n-butylcyclopentadienyl)bis(3-cyanophenoxy)zirconium,bis(n-butylcyclopentadienyl)bis(4-cyanophenoxy)zirconium,bis(tert-butylcyclopentadienyl)bis(2-fluorophenoxy)zirconium,bis(tert-butylcyclopentadienyl)bis(3-fluorophenoxy)zirconium,bis(tert-butylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,bis(tert-butylcyclopentadienyl)bis(2-ethylphenoxy)zirconium,bis(tert-butylcyclopentadienyl)bis(3-ethylphenoxy)zirconium,bis(tert-butylcyclopentadienyl)bis(4-ethylphenoxy)zirconium,bis(tert-butylcyclopentadienyl)bis(2,4-dimethylphenoxy)zirconium,bis(1,3-di-tert-butylcyclopentadienyl)bis(2-chlorophenoxy)zirconium,bis(1,3-di-tert-butylcyclopentadienyl)bis(3-chlorophenoxy)zirconium,bis(1,3-di-tert-butylcyclopentadienyl)bis(4-chlorophenoxy)zirconium,bis(1,3-di-tert-butylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium,bis(1,3-di-tert-butylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium,bis(1,3-di-tert-butylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,bis(phenylcyclopentadienyl)bis(2-phenylphenoxy)zirconium,bis(phenylcyclhpentadienyl)bis(3-phenylphenoxy)zirconium,bis(phenylcyclopentadienyl)bis(4-phenylphenoxy)zirconium,bis(phenylcyclopentadienyl)bis(2,4-dichlorophenoxy)zirconium,bis(trimethylsilylcyclopentadienyl)bis(2-tert-butoxyphenoxy)zirconium,bis(trimethylsilylcyclopentadienyl)bis(3-tert-butoxyphenoxy)zirconium,bis(trimethylsilylcyclopentadienyl)bis(4-tert-butoxyphenoxy)zirconium,bis(trimethylsilylcyclopentadienyl)bis(2-phenylphenoxy)zirconium,bis(trimethylsilylcyclopentadienyl)bis(3-phenylphenoxy)zirconium,bis(trimethylsilylcyclopentadienyl)bis(4-phenylphenoxy)zirconium,bis(trimethylsilylcyclopentadienyl)bis(2,4-di-fluorophenoxy)zirconium,bis(cyclohexylcyclopentadienyl)bis(2-iodophenoxy)zirconium,bis(cyclohexylcyclopentadienyl)bis(3-iodophenoxy)zirconium,bis(cyclohexylcyclopentadienyl)bis(4-iodophenoxy)zirconium,bis(indenyl)bis(2-methylphenoxy)zirconium,bis(indenyl)bis(3-methylphenoxy)zirconium,bis(indenyl)bis(4-methylphenoxy)zirconium,bis(1-methylindenyl)bis(2-fluorophenoxy)zirconium,bis(1-methylindenyl)bis(3-fluorophenoxy)zirconium,bis(1-methylindenyl)bis(4-fluorophenoxy)zirconium,bis(2-methylindenyl)bis(2-bromophenoxy)zirconium,bis(2-methylindenyl)bis(3-bromophenoxy)zirconium,bis(2-methylindenyl)bis(4-bromophenoxy)zirconium,bis(5,6-dimethylindenyl)bis(2-isopropylphenoxy)zirconium,bis(5,6-dimethylindenyl)bis(3-isopropylphenoxy)zirconium,bis(5,6-dimethylindenyl)bis(4-isopropylphenoxy)zirconium,bis(5,6-dimethoxyindenyl)bis(2-cyanophenoxy)zirconium,bis(5,6-dimethoxyindenyl)bis(3-cyanophenoxy)zirconium,bis(5,6-dimethoxyindenyl)bis(4-cyanophenoxy)zirconium,bis(fluorenyl)bis(2-chlorophenoxy)zirconium,bis(fluorenyl)bis(3-chlorophenoxy)zirconium,bis(fluorenyl)bis(4-chlorophenoxy)zirconium,bis(4,5,6,7-tetrahydroindenyl)bis(2-tert-butylphenoxy)zirconium,bis(4,5,6,7-tetrahydroindenyl)bis(3-tert-butylphenoxy)zirconium,bis(4,5,6,7-tetrahydroindenyl)bis(4-tert-butylphenoxy)zirconium,bis(2-methyltetrahydroindenyl)bis(2-nitrophenoxy)zirconium,bis(2-methyltetrahydroindenyl)bis(3-nitrophenoxy)zirconium,bis(2-methyltetrahydroindenyl)bis(4-nitrophenoxy)zirconium,bis(2,7-di-tert-butylfluorenyl)bis(2-trifluoromethylphenoxy)zirconium,bis(2,7-di-tert-butylfluorenyl)bis(3-trifluoromethylphenoxy)zirconium,bis(2,7-di-tert-butylfluorenyl)bis(4-trifluoromethylphenoxy)zirconium,etc.

Further, in the present invention, the transition metal compounds may beused similarly, in which the zirconium atom in the zirconium compound ofthe general formula [1] as exemplified is substituted by a titanium orhafnium atom.

On the other hand, as the transition metal compounds represented by thegeneral formula [2], the following compounds may be exemplified:ethylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium,ethylenebis(indenyl)bis(4-fluorophenoxy)zirconium,ethylenebis(indenyl)bis(4-chlorophenoxy)zirconium,ethylenebis(indenyl)bis(2-fluorophenoxy)zirconium,ethylenebis(3-methylindenyl)bis(4-trifluoromethylphenoxy)zirconium,ethylenebis(3-methylindenyl)bis(4-fluorophenoxy)zirconium,ethylenebis(3-methylindenyl)bis(4-chlorophenoxy)zirconium,ethylenebis(3-methylindenyl)bis(2-fluorophenoxy)zirconium,ethylenebis(5,6-dimethylindenyl)bis(4-trifluoromethylphenoxy)zirconium,ethylenebis(5,6-dimethylindenyl)bis(4-fluorophenoxy)zirconium,ethylenebis(5,6-dimethylindenyl)bis(4-chlorophenoxy)zirconium,ethylenebis(5,6-dimethylindenyl)bis(2-fluorophenoxy)zirconium,ethylenebis(4,7-dimethylindenyl)bis(4-trifluoromethylphenoxy)zirconium,ethylenebis(4,7-dimethylindenyl)bis(4-fluorophenoxy)zirconium,ethylenebis(5,6-dimethoxylindenyl)bis(4-trifluoromethylphenoxy)zirconium,ethylenebis(5,6-dimethoxylindenyl)bis(4-fluorophenoxy)zirconium,ethylenebis(5,6-dihydroindenyl)bis(4-trifluoromethylphenoxy)zirconium,ethylenebis(5,6-dihydroindenyl)bis(4-fluorophenoxy)zirconium,ethylenebis(5,6-dihydroindenyl)bis(4-chlorophenoxy)zirconium,ethylenebis(5,6-dihydroindenyl)bis(2-fluorophenoxy)zirconium,ethylenebis(4,5,6,7-tetrahydroindenyl)bis(4-trifluoromethylphenoxy)zirconium,ethylenebis(4,5,6,7-tetrahydroindenyl)bis(4-fluorophenoxy)zirconium,ethylenebis(4,5,6,7-tetrahydroindenyl)bis(4-chlorophenoxy)zirconium,ethylenebis(4,5,6,7-tetrahydroindenyl)bis(2-fluorophenoxy)zirconium,methylenebis(cyclopentadienyl)bis(2-fluorophenoxy)zirconium,methylenebis(cyclopentadienyl)bis(2-ethylphenoxy)zirconium,methylenebis(methylcyclopentadienyl)bis(3-chlorophenoxy)zirconium,methylenbis(1,3-dimethylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium,methylenbis(n-butylcyclopentadienyl)bis(4-tert-butylphenoxy)zirconium,ethylenbis(3-methylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,ethylenbis(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,ethylenbis(3-isopropylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,ethylenbis(3-isopropylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,ethylenbis(3-tert-butylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,ethylenbis(3-tert-butylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,isopropylidene(cyclopentadienyl)(indenyl)bis(4-trifluoromethylphenoxy)zirconium,isopropylidene(cyclopentadienyl)(indenyl)bis(4-fluorophenoxy)zirconium,isopropylidene(methylcyclopentadienyl)(indenyl)bis(4-trifluoromethylphenoxy)zirconium,isopropylidene(methylcyclopentadienyl)(indenyl)bis(4-fluorophenbxy)zirconium,isopropylidenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium,isopropylidenebis(indenyl)bis(4-fluorophenoxy)zirconium,isopropylidene(cyclopentadienyl)(fluorenyl)bis(4-trifluoromethylphenoxy)zirconium,isopropylidene(cyclopentadienyl)(fluorenyl)bis(4-fluorophenoxy)zirconium,isopropylidene(3-methylcyclopentadienyl)(fluorenyl)bis(4-trifluoromethylphenoxy)zirconium,isopropylidene(3-methylcyclopentadienyl)(fluorenyl)bis(4-fluorophenoxy)zirconium,tetramethylethylidenebis(2-tert-butylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,tetramethylethylidenebis(2-tert-butylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium,dimethylsilylenebis(indenyl)bis(4-fluorophenoxy)zirconium,dimethylsilylenebis(2-methylidenyl)bis(4-trifluoromethylphenoxy)zirconium,dimethylsilylenebis(2-methylindenyl)bis(4-fluorophenoxy)zirconium,dimethylsilylenebis(2-ethlyenylidenyl)bis(4-trifluoromethylphenoxy)zirconium,dimethylsilylenebis(2-ethylindenyl)bis(4-fluorophenoxy)zirconium,dimethylsilylenebis(2-methyl-5-isopropylindenyl)bis(4-trifluoromethylphenoxy)zirconium,dimethylsilylenebis(2-methyl-5-isopropylindenyl)bis(4-fluorophenoxy)zirconium,dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-trifluoromethylphenoxy)zirconium,dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-fluorophenoxy)zirconium,dimethylsilylenebis(2-tert-butylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,dimethylsilylenebis(2-tert-butylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylenebis(2-tert-butyl-4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylenebis(2-isopropyl-4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(2,4,5-trimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylene(2,4-dimethylcyclopentadienyl)(3,5-dimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylene(3-tert-butylcyclopentadienyl)(4-tert-butylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylene(3-methylcyclopentadienyl)(4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylene(2,4-dimethylcyclopentadienyl)(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylene(2,4-dimethylcyclopentadienyl)(4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylene(3,4-dimethylcyclopentadienyl)(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylene(3-tert-butylcyclopentadienyl)(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylene(3-tert-butylcyclopentadienyl)(4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)-zirconium,dimethylsilylene(2,4-dimethylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylene(3-tert-butylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylene(3-methylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylene(cyclopentadienyl)(indenyl)bis(4-trifluoromethylphenoxy)zirconium,dimethylsilylene(cyclopentadienyl)(indenyl)bis(4-fluorophenoxy)zirconium,diphenylsilylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium,diphenylsilylenebis(indenyl)bis(4-fluorophenoxy)zirconium,dibenzylsilylenebis(indennyl)bis(4-trifluoromethylphenoxy)zirconium,dibenzylsilylenebis(indenyl)bis(4-fluorophenoxy)zirconium,methylphenylsilylenebis(2-methylindenyl)bis(4-trifluoromethylphenoxy)zirconium,methylphenylsilylenebis(2-methylindenyl)bis(4-fluorophenoxy)zirconiumu,dimethylsilylenebis(3,4-dimethylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,dimethylsilylenebis(3,4-dimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-trifluoromethylphenoxy)zirconium,dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-fluorophenoxy)zirconium.

The transition metal compounds, in which the zirconium atom of thezirconium compounds as mentioned above of the formula [2] is substitutedby a titanium or hafnium atom, also may be used similarly.

The transition metal compounds according to the present invention may besynthesized by some known processes. The transition metal compoundrepresented by the general formula [1 ] is synthesized, for example, bya process in which the IVA group transition metal compound representedby the general formula [3] is reacted at first with alkyl lithium toform the reactive intermediate compound of the general formula [4].Then, the intermediate compound is reacted with an aromatic hydroxy orthiol compound having a specified substituent represented by the generalformula [5] to form a final transition metal compound according to thereaction equation [6]:

(R_(a) Cp)_(m)(R′_(b) Cp)_(n)MZ_(4−(m+n))  [3]

wherein R_(a) Cp and R′_(b) Cp each represents a grouping having thecyclopentadienyl skeleton, M is titanium, zirconium or hafnium, Z is ahalogen atom, each of a and b is an integer of 0-5, each of m and n isan integer of 0-3, and m+n is an integer of 1-3;

(R_(a) CP)_(m)(R′_(b) Cp), MQ_(4−(m+n))  [4]

wherein (R_(a) Cp) and (R′_(b) Cp), M, a, b, m and n each has the samemeaning as in the general formula [3] and Q represents an alkyl radical;

(4−m−n)H—X—Ar—Y_(c))  [5]

wherein X represents an oxygen or sulphur atom, Ar represents anaromatic ring, Y represents a hydrocarbon radical, a silyl radical, ahalogen atom, a halogenated hydrocarbon radical, a nitrogen-containingorganic radical, an oxygen-containing organic radical or asulphur-containing organic radical, and c is an integer of 1-5;

(R_(a) Cp)_(m)(R′_(b) Cp)_(n)MQ_(4−(m+n))+(4−m−n)H—X—Ar—Y_(c)(R_(a)CP)_(m)(R′_(b) Cp)_(n)M(X—Ar—Y_(c))_(4−(m+n))+(4−m−n)QH  [6]

wherein R_(a) Cp and R′_(b)Cp, M, Q, X, Ar, Y, a, b, m, n and c each hasthe same meaning as in the general formulae [4]-[5].

In the reaction equation [6), the reaction temperature is −78° C. to 100° C., preferably 0° C. to 80° C., and the reaction time is 0.1 to 50hrs, preferably 0.5 to 30 hrs. As a solvent hydrocarbon such as benzene,toluene or xylene; ethers such as tetrahydrofuran and diethylether; anda halogenated hydrocarbon such as chloroform and dichloromethane. Thesereaction solvents may be used generally in an amount within 10 to 500times of the compound of the general formula [3] or [4].

The reaction of the equation [6] proceeds in general quantitatively sothat the compound of the general formula [4] and [5] may be reacted eachother in a stoichiometrically required amount. When the solvent isdistilled off in vacuum from the reaction solution after the reaction,the final transition metal compound is obtained. Of course, after thesolvent is distilled off in vacuum from the solution after the reactionof equation [6], the final compound may be further purified by a processsuch as recrystallization.

As other process for synthesizing the transition metal compoundaccording to the present invention, there may be used a process in whichthe compound of the general formula [3] is reacted directly with analkali metal salt of the compound of the general formula [5] and aprocess, which is described for example in Journal of OrganometallicChemistry 485 (1995) 153-160, i.e. a process in which the compound ofthe formula [3] is reacted directly with the compound of the formula (5)in the presence of base compound such as an amine.

On the other hand, the transition metal compound represented by thegeneral formula [2] may be synthesized in the same manner as in theprocess for synthesizing the compound of the general formula [1].

The catalyst for the polymerization of olefins according to the presentinvention is characterized by using as co-catalyst an organic aluminumoxy compound or a cation generator and, if necessary, an organicaluminum compound in combination of said transition metal compound.

The organic aluminum oxy compound may be selected from the linearalkylaluminoxanes of the general formula [7] and the cyclicalkylaluminoxanes of the general formula [8].

Wherein R¹ represents a hydrogen atom, a halogen atom or an alkylradical having 1 to 10 carbon atoms and m is an integer of 2 to 40.

Wherein R¹ and m each has the same meaning in the general formula [7].

As to R¹ in the general formulae [7] and [8], the halogen atom is achlorine or bromine atom and the alkyl radical having 1-10 carbon atomsis methyl, ethyl, iso-butyl and the like. The compound of the formulae[7] and [8] may be contain different R¹ radical therein. Preferably, thecompound has above all methyl or methyl and other radicals. The numberof repeating unit, m, is selected from within the range of 2-40,preferably 5-20.

Various known processes may be used for the synthesis of thealkylalminoxanes of the formulae [7] and [8]. For example, the compoundsmay be synthesized by a process in which a trialkyl aluminum isdissolved in a hydrocarbon solvent and hydrolyzed by adding gradually anequivalent amount of water to the trialkyl aluminum in the solution; aprocess in which a hydrate of copper sulfate or aluminum sulfate issuspended in a hydrocarbon solvent and a trialkyl aluminum in an amountof 1-3 times equivalent to the crystal water of said hydrate in thesuspension is contacted to the hydrate to hydrolyze gradually thetrialkylaluminum; or a process in which the adsorption water ofundehydrated silica gel suspended in a hydrocarbon solvent is contactedto a trialkyl aluminum in an amount of 1 to 3 times equivalent to saidadsorption water to hydrolyze gradually the trialkyl aluminum.

On the other hand, as the cation generator among the co-catalyst, thereare mentioned those of the neutral and ion-pair type; those of neutraltype include, for example, the organic boron compounds represented bythe general formula [9]

BR² ₃  [9]

wherein R² represents a hydrogen atom, a hydrocarbon radical having 1 to20 carbon atoms or a halogen atom.

Preferably, the compounds of the general formula [9] are especiallythose, in which a hydrocarbon radical to be bonded to the boron atom.The three R² radical may be same or different and except for hydrocarbonradicals, a part of three R² may be substituted by a hydrogen or halogenatom.

Examples of R² include an alkyl radical such as methyl, ethyl, n-propyl,iso-butyl and n-octyl; or an aryl radical such as phenyl and tolyl.

Concrete examples of the organic boron compounds of the formula [9]include triphenylborane, tris(pentafluorophenyl)borane,tris(2,3,4,5-tetrafluorophenyl)borane,tris(2,4,6-trifluorophenyl)borane, tris(2,3-difluorophenyl)borane,tris(2-fluorophenyl)borane, tris[3,5-bis(trifluoromethyl)phenyl]borane,tris[4-(trifluoromethyl)phenyl]borane, trimethylborane, triethylborane,tris(trifluoromethyl)borane, diphenylfluoroborane,bis(pentafluorophenyl)chloroborane. Of these, prefered ones aretris(pentafluorophenyl]borane andtris[3,5-bis(trifluoromethyl)phenyl]borane.

The ion pair type cation generators are compounds of the formula [10].

[On]⁺[BR³ ₄]⁻  [10]

wherein [On]⁺is a metal cation of group 1B, 2B, or 8, carbenium ion,silicenium ion, oxonium ion, sulfonium ion, ammonium ion or phosphoniumion, and R³ is a hydorocarbon radical having 1 to 20 carbon atoms,respectively.

Concrete examples of the cation generators of the formula [10] includesalts of tetrakis(pentafluorophenyl)borate, such as ferroceniumtetrakis(pentafluorophenyl)borate, silver (I)tetrakis(pentafluorophenyl)borate, copper (I)tetrakis(pentafluorophenyl)borate, marcury (II)bis[tetrakis(pentafluorophenyl)]borate, palladium (II)bis[tetrakis(pentafluorophenyl)]borate, platinum (II)bis[tetrakis(pentafluorophenyl)]borate, diphenylhydorocarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, tricyclohexylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylsiliceniumtetrakis(pentafluorophenyl)borate, triethyloxoniumtetrakis(pentafluorophenyl)borate, triethylsulfoniumtetrakis(pentafluorophenyl)borate, diethylaniliniumtetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tetra-n-butylammoniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate.

In the practice of the present invention, the organic aluminum compoundrepresented by the general formula [11] may be co-existed, if necessary,in order to stabilize the catalyst or in order to stabilize the organicaluminum oxy compound or cation generator as the above-mentionedco-catalyst and reduce the amount to be used.

R⁴ ₃ A1  [11]

wherein R⁴ represents a hydrogen atom, an alkyl radical having 1-10carbon atoms or a halogen atom, proviso that all R⁴ radicals are nothydrogen or halogen atoms.

R⁴ as an alkyl radical having 1-10 carbon atoms is, for example, methyl,ethyl, iso-butyl or octyl radical and as a halogen atom is, for example,a chlorine or bromine atom. Further, the radical R⁴ of the compoundsrepresented by the general formula [11] may be same or different.

As the compounds of the formula [11], there may be mentioned, forinstance, trimethylaluminum, triethylaluminum, triisobutylaluminum,trihexylaluminum, trioctylaluminum, diisobutylaluminum hydride,diethtylaluminum chloride, ethylaluminum sesquichloride.

In the practice of the polymerization of olefines in the presentinvention, the catalyst for the polymerization may be prepared by addingthe transition metal compound according to the present invention ascatalyst component and an organic aluminum oxy compound or cationgenerator as a co-catalyst, and if necessary, an organic aluminumcompound to an inert hydrocarbon solvent or an olefin medium to bepolymerized. Then, the addition order of each component may be selectedoptionally, the transition metal compound and co-catalyst may be usedafter mixing and contacting them for a certain time before thepolymerization previously, or each component may be also addedrespectively to the polymerization system.

The transition metal compound according to the present invention for thepolymerization of olefins is used in general in a catalyst concentrationwithin the range of 10⁻⁸-18-10⁻¹ mol/liter, preferably 10⁻⁷-10⁻³mol/liter. On the other hand, the organic aluminum oxy compound asco-catalyst is used in general within the range of 10-10⁵, preferably 50to 5×10³ of the ratio of aluminum atom/transition metal atom. The cationgenerator as co-catalyst is used in general within the range of 0.5 to10, preferably 1 to 5 of the mol ratio of cation generator/transitionmetal compound. The organic aluminum compound of the general formula(11) is used in general within the range of 1 to 10⁵, preferably 10 to10⁴ of the ratio of aluminum atom/transition metal atom.

The polymerization according to the present invention can be carried outby means of every polymerization process such as the slurry, solution orgas-phase polymerization. In the slurry or gas-phase polymerization,either the catalyst component of the transition metal compound or theco-catalyst or both of them may be deposited on a support for use.Examples of support include, for example, an inorganic oxide supportsuch as silica, alumina or silica-alumina; an inorganic support such asmagnesium chloride; and an organic support such as polyethylene andpolypropylene. The method for supporting on a support is not criticaland any known method may be used. The catalyst supported on a supportmay be subjected to the so-called prepolymerization treatment, in whicha relatively small amount of olefin is previously polymerized in thepolymerization of olefines, where the amount of olefin polymer to beproduced is preferably up to 0.05 to 500 g, preferably up to 0.1 to 100g per g of the carried catalyst. A process in which either the catalystcomponent or the co-catalyst or both of them is supported on a supportand used, or a process in which either the catalyst component or theco-catalyst or both of them is used after the prepolymerization, is aavailable especially for the slurry or gas-phase polymerization becausethe particle shape and bulk density of the polymer produced are improvedand the like.

Olefins to be used in the process according to the present inventioninclude not only α-olefins but also those other than α-olefins forexample, linear diolefins, cyclic olefins, cyclic polyenes, aromaticvinyl compounds, or the like.

As alpha-olefins, those having 2 to 20 carbon atoms are particularlymentioned. For instance, ethylene, propylene, 1-butene,3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene,3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene, 1-tetradecene, 1-hexadecene, 1-octadecene,1-eicocene, vinylcyclohexane, vinylcyclohexene, trimethylvinylsilane maybe mentioned.

Linear diolefins are, particularly, those having 4 to 20 carbon atoms.For instance, non-conjugated dienes, such as 1,4-pentadiene,1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene,5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 1,7-octadiene,7-methyl-1,6-octadiene and: 1,9-decanediene, or conjugated dienes, suchas butadiene, isoprene, chloroprene, 1,3-pentadiene and 1,3-hexadienemay be mentioned.

Cyclic olefins are, particularly, those having 4 to 40 carbon atoms. Forinstance, cyclobutene, cyclopentene, cyclohexene, cycloheptene,cyclooctene, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene,5-chloro-2-norbornene, 5-methoxy-2-norbornene, 5,6-dicarboxylnorborneneanhydrate, tetracyclododecene, 5-phenylnorbornene may be mentioned.

Cyclic polyenes are, particularly, those having 5 to 40 carbon atoms.For instance, cyclopentadiene, dicyclopentadiene, norbornadiene,5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, cyclooctatriene may bementioned. As aromatic vinyl compounds, for instance, styrene,alpha-methylstyrene, divinylbenzene are usable.

These olefins may be homopolymerized and two or more than two olefinsmay be copolymerized.

In the present invention, an inert hydrocarbon solvent or the olefinitself to be polymerized may be used for carring out the solution orslurry polymerization. As inert hydrocarbon solvents, there may be used,for example, an aliphatic hydrocarbon such as butane, isobutane,pentane, hexane, octane, an alicyclic hydrocarbon such as cyclopentane,methylcyclopentane or cyclohezane; an aromatic hydrocarbon such asbenzene, toluene or zylene; and a petroleum fraction such as naphtha,kerosene or light oil.

The polymerization temperature in the practice of the polymerization ofthe present invention is in general within the range of −20 to 100° C.,preferably 20 to 90° C. in the slurry polymerization, and in generalwithin the range of 0 to 120° C., preferably 20 to 100° C. in thegas-phase polymerization; it is in general within the range of 0 to 300°C., preferably 100 to 250° C. in the solution polymerization. Thepolymerization pressure is not critical, but is used in general withinthe range from a atomospheric pressure to 100 kg/cm².

The polymerization according to the present invention may be carried outin a batch, semi-continuous or continuous method and in two or more thantwo steps of different reaction condition. The molecular weight (weightaverage molecular weight) of olefin polymer obtained by using thecatalyst according to the present invention is in general 1,000 to10,000,000, especially 5,000 to 5,000,000. The molecular weight ofolefin polymer obtained may be controlled by the presence of hydrogen inthe polymerization reaction system or the change of polymerizationtemperature.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow chart illustrating the preparation steps of thecatalyst according to the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be explained in detail hereinafter byexamples, by which the present invention is not limited thereto only.

In the synthesis of the transition metal compounds in the followingexamples, the transition metal compounds represented by the generalformula [4] used as the starting material are those, which are availablecommercially or are prepared by the method described in literature (forexample, Journal of American Chemical Society 95 (1973) 6263-6267).

The aromatic hydroxy or thiol compounds represented by the generalformula [5] as another starting material are those, which are availablecommercially.

All preparative reactions were carried out under an argon atmosphereusing a standard Schlenk technique.

The yield is calculated based on the transition metal compound asstarting material and shown in % (by weight). The resulting transitionmetal compound was identified by means of ¹H-NMR spectroscopy (δ (unit:ppm)) and the elementary analysis (unit: % by weight).

The dilution of catalyst component and the operation of polymerizationand the like were carried out under argon atmosphere. The comonomercontent in the copolymer was determined by means of ¹³C-NMRspectroscopy.

I. Synthesis of Catalyst Component EXAMPLE 1 Synthesis of CatalystComponent (a)-1 (Dicyclopentadienylbis(2-methylphenoxy)zirconium)

To a 50 ml Schlenk tube having been sufficiently exchanged by argon, 10ml of toluene solution containing 106.0 mg of dicyclopentadienyldimethylzirconium and 90.6 mg of orthocresol were added and the resultantmixture was stirred at room temperature for 1 hr. After the completionof reaction, toluene was distilled off under reduced pressure to yield atransition metal compound of white solid (catalyst component (a)-1). Theyield amount of the catalyst component (a)-1 was 176.7 mg correspondingto 99% yield.

The results of the ¹H-NMR spectoroscopy (measured in C₆D₆) and theelementary analysis of the product were as follows:

¹H-NMR spectral data: δ 2.23(s, 6H), 5.94 (s, 10H), 6.67 (d, 2H, J=7.6Hz), 6.89(d, 2H, J=7.2 Hz) 7.18(d, 2H, J=7.4 Hz), 7.19(d, 2H, J=7.4 Hz),elementary analysis: C 66.02, H 5.78, Zr 20.65.

By the results as mentioned above, the catalyst component (a)-1 wasconfirmed as dicyclopentadienylbis(2-methylphenoxy)zirconium.

EXAMPLES 2 TO 68 Synthesis of Catalyst Components (a)-2 to (a)-68

The same reaction as well as treatment after the reaction was carriedout as in Example 1 except that the phenol compound to be reacted withdicyclopentadienyldimethyl zirconium was exchanged from orthocresol tothe substituted phenol compounds as shown in Tables 1 to 5 and theamount of each starting material used was shown in Tables 1 to 5. Theresulting transition metal compounds were shown as catalyst component(a)-2 to (a)-68 respectively. The yield amount, yield and appearance ofeach catalyst component are summarized in Tables 1 to 5. Each productwas confirmed as the final transition metal compound by the results ofelementary analysis and ¹H-NMR spectoroscopy. The results are summarizedin Tables 6 to 13.

TABLE 1 Cp₂ZrMe₂ Substituted Yield Example Catalyst (used amount) phenolUsage amount Yield No. component (mg) compound (mg) (%) (%) AppearanceEx. 1 (a)-1 106.0 o-cresol 90.6 181.0 99 white solid Ex. 2 (a)-2 118.9m-cresol 101.7 154.5 75 colorless crystal Ex. 3 (a)-3 111.8 p-cresol95.6 132.1 69 colorless crystal Ex. 4 (a)-4 102.9 2-methoxyphenol 108.0188.0 99 colorless oil Ex. 5 (a)-5 97.3 3-methoxyphenol 95.3 181.4 100yellow oil Ex. 6 (a)-6 89.2 4-methoxyphenol 87.4 161.3 99 white solidEx. 7 (a)-7 147.3 2-trifluoromethyl- 188.7 253.3 80 colorless phenolcrystal Ex. 8 (a)-8 105.6 3-trifluoromethyl- 125.0 228.2 99 white phenolsolid Ex. 9 (a)-9 131.5 4-trifluoromethyl- 168.3 189.2 67 colorlessphenol crystal Ex. 10 (a)-10 97.5 2-cyanophenol 92.4 175.8 99 red solidEx. 11 (a)-11 116.3 3-cyanophenol 110.2 195.6 93 colorless crystal Ex.12 (a)-12 112.5 4-cyanophenol 106.5 206.6 100 white solid Ex. 13 (a)-13132.4 2-nitrophenol 146.5 200.1 76 yellow crystal Ex. 14 (a)-14 116.13-nitrophenol 128.4 168.3 73 yellow crystal Ex. 15 (a)-15 100.44-nitrophenol 110.1 188.5 95 yellow crystal Ex. 16 (a)-16 148.22-chlorophenol 151.4 277.9 99 colorless oil

TABLE 2 Cp₂ZrMe₂ Substituted Yield Example Catalyst (used amount) phenolUsage amount Yield No. component (mg) compound (mg) (mg) (%) AppearanceEx. 17 (a)-17 110.9 3-chlorophenol 113.4 177.0 84 colorless crystal Ex.18 (a)-18 116.2 4-chlorophenol 119.0 220.2 100 white solid Ex. 19 (a)-19207.1 2-fluorophenol 183.4 359.5 99 white solid Ex. 20 (a)-20 212.23-fluorophenol 187.9 295.5 79 colorless crystal Ex. 21 (a)-21 209.74-fluorophenol 185.6 374.4 100 white solid Ex. 22 (a)-22 83.32-bromophenol 113.8 191.6 100 colorless oil Ex. 23 (a)-23 80.63-bromophenol 110.0 187.0 100 white solid Ex. 24 (a)-24 84.74-bromophenol 115.9 191.4 100 colorless oil Ex. 25 (a)-25 53.62-iodophenol 93.3 142.5 100 yellow oil Ex. 26 (a)-26 58.8 3-iodophenol102.1 155.9 100 white solid Ex. 27 (a)-27 62.1 4-iodophenol 107.8 162.8100 colorless oil Ex. 28 (a)-28 73.8 2-ethylphenol 71.3 138.9 100 yellowoil Ex. 29 (a)-29 73.6 3-ethylphenol 71.1 135.5 100 colorless oil Ex. 30(a)-30 76.2 4-ethylphenol 73.5 138.5 99 colorless oil Ex. 31 (a)-31 70.12-isopropylphenol 75.4 136.4 100 colorless oil Ex. 32 (a)-32 76.63-isopropylphenol 82.5 147.7 99 colorless oil

TABLE 3 Cp₂ZrMe₂ Substituted Yield Example Catalyst (used amount) phenolUsage amount Yield No. component (MG) compound (mg) (mg) (%) AppearanceEx. 33 (a)-33 76.5 4-isopropylphenol 82.3 146.4 99 colorless oil Ex. 34(a)-34 70.6 2-tert-butylphenol 83.8 149.1 100 colorless oil Ex. 35(a)-35 68.7 3-tert-butylphenol 81.4 142.7 100 colorless oil Ex. 36(a)-36 68.4 4-tert-butlphenol 81.1 140.9 100 white solid Ex. 37 (a)-37104.9 2,3-difluorophenol 109.0 206.0 100 white solid Ex. 38 (a)-38 134.02,4-difluorophenol 137.6 251.2 99 white solid Ex. 39 (a)-39 90.02,5-difluorophenol 93.6 170.0 99 white solid Ex. 40 (a)-40 164.72,6-difluorophenol 169.4 309.0 99 white solid Ex. 41 (a)-41 89.63,4-difluorophenol 93.0 169.7 100 white solid Ex. 42 (a)-42 101.33,5-difluorophenol 105.0 190.1 99 white solid Ex. 43 (a)-43 83.22,3,4-trifluoro- 96.6 134.5 80 colorless phenol crystal Ex. 44 (a)-4486.2 2,3,6-trifluoro- 101.1 71.4 41 colorless phenol crystal Ex. 45(a)-45 97.5 2,4,5-trifluoro- 115.0 205.3 100 white phenol solid Ex. 46(a)-46 100.6 2,4,6-trifluoro- 118.1 205.1 100 white phenol solid Ex. 47(a)-47 233.8 2,3,5,6-tetra- 306.9 451.5 89 colorless fluorophenolcrystal Ex. 48 (a)-48 304.7 pentafluorophenol 441.7 387.3 55 colorlesscrystal

TABLE 4 Cp₂ZrMe₂ Substituted Yield Example Catalyst (used amount) phenolUsage amount Yield No. component (mg) compound (mg) (mg) (%) AppearanceEx. 49 (a)-49 65.1 2-phenylphenol 87.5 105.0 73 white crystal Ex. 50(a)-50 73.4 3-phenylphenol 98.7 166.2 100 yellow oil Ex. 51 (a)-51 64.14-phenylphenol 86.2 98.2 69 white crystal Ex. 52 (a)-52 90.5 2-hydroxy-97.2 174.7 99 yellow acetophenone oil Ex. 53 (a)-53 100.7 3-hydroxy-108.1 200.7 100 colorless acetophenone oil Ex. 54 (a)-54 89.2 4-hydroxy-95.8 74.4 43 white acetophenone crystal Ex. 55 (a)-55 72.3 methylsalicylate 87.0 151.9 100 yellow oil Ex. 56 (a)-56 69.1 methyl3-hydroxy- 83.1 143.5 100 colorless benzoate oil Ex. 57 (a)-57 69.0methyl 4-hydroxy- 83.1 76.3 53 white benzoate crystal Ex. 58 (a)-58121.5 2,4-dichlorophenol 156.5 154.5 59 white crystal Ex. 59 (a)-59101.4 2,4-dimethylphenol 98.0 188.6 100 colorless oil Ex. 60 (a)-60 74.52-chloro-4-trifluoro- 123.6 191.4 100 colorless methylphenol oil Ex. 61(a)-61 62.5 2-chloro- 74.5 125.8 99 white 4-fluorophenol crystal Ex. 62(a)-62 52.2 2-chloro- 72.0 95.7 82 yellow 4-nitrophenol crystal Ex. 63(a)-63 53.6 2-fluoro- 66.8 98.4 87 yellow 4-nitrophenol crystal Ex. 64(a)-64 66.9 2-methyl-4- 69.9 64.7 52 white fluorophenol crystal

TABLE 5 Cp₂ZrMe₂ Substituted Yield Example Catalyst (used amount) phenolUsage amount Yield No. component (mg) compound (mg) (mg) (%) AppearanceEx. 65 (a)-65 79.3 1-naphthol 89.8 100.1 63 white crystal Ex. 66 (a)-6676.2 2-naphthol 86.7 73.3 48 white crystal Ex. 67 (a)-67 90.82-fluorothiophenol 92.0 110.0 64 yellow crystal Ex. 68 (a)-68 74.02-chlorothiophenol 84.5 148.5 100 yellow solid

TABLE 6 Elementary analysis Catalyst (wt %) ¹H-NMR spectral datacomponent C H Zr (δ: p p m) (a)-1 66.02 5.78 20.65 δ 2.23(s, 6H),5.94(s, 10H), 6.67(d, 2H, J = 7.6 Hz), 6.89 (d, 2H, J = 7.2 Hz), 7.18(d,2H, J = 7.4 Hz), 7.19(d. 2H, J = 7.4 Hz) (a)-2 66.13 5.62 20.78 δ2.26(s, 6H), 6.00(s, 10H), 6.65(d, 2H, J = 8.1 Hz), 6.73 (s, 2H),6.74(d, 2H, J = 8.5 Hz), 7.21(d, 2H, J = 7.7 Hz) (a)-3 66.10 5.65 20.87δ 2.25(s, 6H), 6.00(s, 10H), 6.75(d, 4H, J = 8.3 Hz), 7.08 (d, 4H, J =8.3 Hz) (a)-4 61.33 5.43 19.39 δ 3.44(s, 6H), 6.13(s, 10H), 6.74(d, 2H,J = 7.9 Hz), 6.82-6.86(m, 2H), 6.95-6.98(m, 4H) (a)-5 61.58 5.31 19.33 δ3.45(s, 6H), 5.99(s, 10H), 6.45-6.59(m, 6H), 7.17 (s, 2H)

TABLE 7 Elementary analysis Catalyst (wt %) ¹H-NMR spectral datacomponent C H Zr (δ : p p m) (a)-6 61.43 5.44 19.41 δ 3.45(s, 6H),6.02(s, 10H), 6.73(d, 4H, J = 8.9Hz), 6.89(d, 4H, J = 8.9 Hz) (a)-753.00 3.42 16.65 δ 6.02(s, 10H), 6.60(t, 2H, J = 7.6 Hz), 6.70(d, 2H, J= 8.2 Hz), 7.08(t, 2H, J = 7.8 Hz), 7.47(dd, 2H, J = 7.8&1.3Hz) (a)-852.87 3.56 16.85 δ 5.79(s, 10H), 6.68(d, 2H, J = 7.8 Hz), 7.03(t, 2H, J= 7.8 Hz), 7.08(s, 2H), 7.09(d, 2H, J = 7.8 Hz) (a)-9 52.91 3.68 16.50 δ5.82(s, 10H), 6.50(d, 4H, J = 8.5 Hz), 7.50(d, 4H, J = 8.5 Hz) (a)-1062.80 4.08 19.71 δ 6.12(s, 10H), 6.43(dt, 2H, J= 7.5&1.0 Hz), 6.73(d,2H, J = 8.3 Hz), 7.05(ddd, 2H, J = 8.3, 7.5&1.7 Hz), 7.14(dd, 2H, J =7.5&1.7 Hz) (a)-11 62.87 4.05 19.87 δ 5.72(s, 10H), 6.54-6.58(m, 2H),6.73(s, 2H), 6.79- 6.83(m, 4H) (a)-12 62.73 4.20 19.68 δ 5.80(s, 10H),6.30(d, 4H, J= 8.4 Hz), 7.23(d,4H, J = 8.4 Hz) (a)-13 53.03 3.87 18.12 δ5.97(s, 10H), 6.41(ddd, 2H, J = 8.3, 7.5,&1.2 Hz), 6.70(dd, 2H, J =8.3&1.2 Hz), 6.99(ddd, 2H, J = 8.2, 1.5& 1.7 Hz), 7.69(dd, 2H, J =8.2&1.7 Hz) (a)-14 52.98 3.98 18.19 δ 5.77(s, 10H), 6.70(ddd, 2H, J =7.0, 2.3&0.8 Hz), 6.87 (t, 2H, J = 8.1 Hz), 7.52(t, 2H, J = 2.3 Hz),7.67(ddd, 2H, J = 8.1, 2.3&1.0 Hz)

TABLE 8 Elementary analysis Catalyst (wt %) ¹H-NMR spectral datacomponent C H Zr (δ : p p m) (a)-15 53.08 3.72 18.29 δ 5.73(s, 10H),6.22(d, 4H, J = 9.0 Hz), 8.12(d, 4H, J = 9.0 Hz) (a)-16 55.30 4.00 19.01δ 6.02(s, 10H), 6.60(dt, 2H, J = 7.6&1.6 Hz), 6.85(dd, 2H, J = 8.1&1.6Hz), 6.99(ddd, 2H, J = 8.1, 7.6&1.6 Hz), 7.14(dd, 2H, J = 7.9&1.6 Hz)(a)-17 55.32 3.99 19.09 δ 5.80(s, 10H), 6.49(dt, 2H, J = 7.7&1.7 Hz),6.83(t, 2H, J = 2.1 Hz), 6.88-6.95(m, 4H) (a)-18 55.24 4.11 19.00 δ5.85(s, 10H), 6.44(d, 4H, J = 8.7 Hz), 7.19(d, 4H, J = 8.7 Hz) (a)-1959.06 4.27 20.21 δ 6.01(s, 10H), 6.62(m, 2H), 6.90(m, 4H), 7.02(m, 2H)(a)-20 59.23 4.11 20.43 δ 5.86(s, 10H), 6.43(ddd, 2H, J = 8.2, 2.3&0.8Hz), 6.5 6.50(dt, 2H, J = 10.9&2.3 Hz), 6.43(tdd, 2H, J = 8.2, 2.4& 0.8Hz), 6.99(dt, 2H, J = 8.1&7.3 Hz) (a)-21 59.40 4.16 20.31 δ 5.92(s,10H), 6.48(dd, 4H, J = 8.9&4.6 Hz), 6.91(dd, 4H, J = 8.9&8.8 Hz) (a)-2246.56 3.46 16.04 δ 6.05(s, 10H), 6.53(ddd, 2H, J = 8.0, 7.2&1.6 Hz),6.84 (dd, 2H, J = 8.0&1.6 Hz), 7.00(ddd, 2H, J = 8.0, 7.2&1.6 Hz),7.52(dd, 2h, J = 8.0&1.6 Hz) (a)-23 46.36 3.31 16.00 δ 5.79(s, 10H),6.51(ddd, 2H, J = 8.0, 2.1&1.1 Hz), 6.86 (t, 2H, J = 8.0 Hz), 7.01(t,2H, J = 2.1 Hz), 7.03(ddd, 2H, J = 8.0, 2.1&1.1 Hz)

TABLE 9 Elementary analysis Catalyst (wt %) ¹H-NMR spectral datacomponent C H Zr (δ : p p m) (a)-24 46.65 3.38 16.07 δ 5.84(s, 10H),6.38(d, 4H, J = 8.8 Hz), 7.33(d, 4H, J = 8.8 Hz) (a)-25 39.88 2.96 13.69δ 6.10(s, 10H), 6.40(ddd, 2H, J = 7.8, 7.2&1.5 Hz), 6.80 (dd, 2H, J =8.0&1.5 Hz), 7.03(ddd, 2H, J = 8.0, 7.2&1.6 Hz), 7.75(dd, 2H, J =7.8&1.6 Hz) (a)-26 39.92 3.06 13.69 δ 5.78(s, 10H), 6.55(ddd, 2H, J =8.0, 2.2&1.1 Hz), 6.72 (t, 2H, J = 8.0 Hz), 7.22(ddd, 2H, J = 8.0,2.1&1.1 Hz), 7.24(t, 2H, J = 2.2 Hz) (a)-27 40.02 2.89 13.70 δ 5.83(s,10H), 6.29(d, 4H, J = 8.7 Hz), 7.51(d, 4H, J = 8.7 Hz) (a)-28 67.56 5.8119.49 δ 1.27(t, 6H, J = 7.6 Hz), 2.68(q, 4H, J = 7.6 Hz), 5.98(s, 10H),6.65(dd, 2H, J = 7.7&1.1 Hz), 6.93(dt, 2H, J = 7.7, 7&1.1 Hz),7.17-7.23(m, 4H) (a)-29 67.20 6.19 19.84 δ 1.22(t, 6H, J = 7.6 Hz),2.59(q, 4H, J = 7.6 Hz), 6.02(s, 10H), 6.65-6.69(m, 2H), 6.76-6.80(m,4H), 7.24(t, 2 H, J = 7.8 Hz) (a)-30 67.22 6.08 19.96 δ 1.21(t, 6H, J =7.6 Hz), 2.58(quint, 4H, J = 7.6 Hz), 6.00(s, 10H), 6.79(d, 4H, J = 8.4Hz), 7.12(d, 4H, J = 8.4 Hz) (a)-31 68.31 6.69 18.41 δ 1.32(d, 12H, J =6.9 Hz), 3.44(quint, 2H, J = 6.9 Hz), 6.01(s, 10H), 6.61(dd, 2H, J =7.8&1.2 Hz), 6.97(dt, 2H, J = 7.8, 7.8&1.2 Hz), 7.18(dt, 2H, J = 7.8,7.8&1.8 Hz), 7.28(dd, 2H, J = 7.8&1.8 Hz)

TABLE 10 Elementary analysis Catalyst (wt %) ¹H-NMR spectral datacomponent C H Zr (δ : p p m) (a)-32 67.99 6.68 18.27 δ 1.27(d, 12H, J =6.9 Hz), 2.83(quint, 2H, J = 6.9 Hz), 6.03(s, 10H), 6.66(ddd, 2H, J =7.8, 2.1&1.0 Hz), 6.81(d, 2H, J = 7.8 Hz), 6.84(t, 2H, J = 2.1 Hz),7.26(t, 2H, J = 7.8 Hz) (a)-33 68.18 6.87 18.41 δ 1.26(d, 12H, J = 6.9Hz), 2.84(quint, 2H, J = 6.9 Hz), 6.00(s, 10H), 6.81(d, 4H, J = 8.5 Hz),7.17(d, 4H, J = 8.5 Hz) (a)-34 69.21 7.11 17.36 δ 1.50(s, 18H), 6.11(s,10H), 6.77(dd, 2H, J = 7.8&1.4 Hz), 6.88(dt, 2H, J = 7.8, 7.8&1.4 Hz),7.07(dt, 2H, J = 7.8, 7.8&1.7 Hz), 7.34(dd, 2H, J = 7.8&1.7 Hz) (a)-3569.17 7.06 17.65 δ 1.35(s, 18H), 6.04(s, 10H), 6.67(ddd, 2H, J = 7.9&2.1&1.0 Hz), 6.98(ddd, 2H, J = 7.9, 2.1&1.0 Hz), 7.03(t, 2 H, J = 2.1 Hz),7.28(t, 2H, J = 7.9 Hz) (a)-36 69.09 7.24 17.46 δ 1.34(s, 18H), 6.02(s,10H), 6.82(d, 4H, J = 8.6 Hz), 7.35(d, 4H, J = 8.6 Hz) (a)-37 55.08 3.2619.00 (a)-38 55.03 3.31 18.99 δ 5.94(s, 10H), 6.56-6.64(m, 4H),6.70-6.77(m, 2H) (a)-39 55.19 3.38 19.14 (a)-40 54.99 3.53 18.92 (a)-4154.91 3.39 18.97 (a)-42 54.90 3.44 19.03

TABLE 11 Elementary analysis Catalyst (wt %) ¹H-NMR spectral datacomponent C H Zr (δ : p p m) (a)-43 51.03 2.99 17.59 (a)-44 51.19 2.8617.55 (a)-45 51.14 3.01 17.53 (a)-46 51.16 3.00 17.58 (a)-47 47.81 2.2416.50 δ 5.89(s, 10H), 6.07(m, 2H) (a)-48 44.90 1.77 15.51 δ 5.85(s, 10H)(a)-49 72.88 5.13 16.21 δ 5.70(s, 10H), 6.79(dd, 2H, J = 7.5&1.2 Hz),6.92(dt, 2H, J = 7.5, 7.5&1.2 Hz), 7.13(dt, 2H, J = 7.5, 7.5&1.6 Hz),7.21(dt, 2H, J = 7.6, 7.6&1.5 Hz), 7.23(t, 4H, J = 7.6 Hz), 7.35(dd, 2H,J = 7.5&1.6 Hz), 7.50(dd, 4H, J = 7.6&1.5 Hz) (a)-50 72.99 5.32 16.18 δ5.99(s, 10H), 6.78(ddd, 2H, J = 7.8, 2.4&1.0 Hz), 7.11- 7.25(m, 10H),7.30(t, 2H, J = 7.8 Hz), 7.65(dd, 4H, J = 8.3&1.3 Hz) (a)-51 73.06 4.9716.09 δ 6.01(s, 10H), 6.86(d, 4H, J = 8.6 Hz), 7.29(t, 4H, J = 7.7 Hz),7.59(d, 4H, J = 8.6 Hz), 7.63(dd, 4H, J = 7.7&1.3 Hz) (a)-52 63.46 4.8818.25 (a)-53 63.32 5.02 18.36 δ 2.25(s, 6H), 5.92(s, 10H), 6.92(ddd, 2H,J = 7.7, 2.4 &1.0 Hz), 7.13(t, 2H, J = 7.7 Hz), 7.31(ddd, 2H, J = 7.7,1.6&1.0 Hz), 7.59(dd, 2H, J = 2.4&1.6 Hz)

TABLE 12 Elementary analysis Catalyst (wt %) ¹H-NMR spectral datacomponent C H Zr (δ : p p m) (a)-54 63.39 5.07 18.40 δ 2.26(s, 6H),5.89(s, 10H), 6.62(d, 4H, J = 8.7 Hz), 8.01(d, 4H,1 = 8.7 Hz) (a)-5559.43 4.87 17.31 (a)-56 61.00 4.69 16.34 δ 3.56(s, 6H), 5.89(s, 10H),6.89(ddd, 2H, J = 7.8, 2.4 &1.0 Hz), 7.12(t, 2H, J = 7.8 Hz), 7.72(dd,2H, J = 2.4&1.8 Hz), 7.83(ddd, 2H, J = 7.8, 1.8&1.0 Hz) (a)-57 59.514.88 17.36 δ 3.61(s, 6H), 5.83(s, 10H), 6.61(d, 4H, J = 8.6 Hz), 8.30(d,4H, J = 8.6 Hz) (a)-58 48.37 3.10 16.51 δ 5.91(s, 10H), 6.50(d, 2H, J =8.6 Hz), 6.96(dd, 2H, J = 8.6&2.5 Hz), 7.35(d, 2H, J = 2.5 Hz) (a)-5967.22 6.44 18.47 δ 2.25(s, 6H), 2.28(s, 6H), 5.98(s, 5H), 6.09(s, 5H),6.65(d, 2H, J = 8.5 Hz), 6.99(s, 2H), 7.01(d, 2H, J = 8.5 Hz) (a)-6047.02 2.89 14.54 δ 5.87(s, 10H), 6.55(dd, 2H, J = 8.9&0.5 Hz), 7.26(ddd,2H, J = 8.9, 2.3&0.5 Hz), 7.68(d, 2H, J = 2.3 Hz) (a)-61 51.67 3.1517.63 δ 5.95(s, 10H), 6.53(dd, 2H, J = 8.9&5.3 Hz), 6.68(ddd, 2H, J =8.9, 8.0&3.1 Hz), 7.06(dd, 2H, J = 8.0&3.1 Hz) (a)-62 46.42 3.00 16.07 δ5.80(s, 10H), 6.28(d, 2H, J = 9.0 Hz), 7.86(dd, 2H, J = 9.0&2.8 Hz),8.25(d, 2H, J = 2.8 Hz) (a)-63 49.37 3.11 16.92 δ 5.78(s, 10H), 6.34(t,2H, J = 8.8 Hz), 7.82(ddd, 2H, J = 8.8, 2.5&1.1 Hz), 7.88(dd, 2H, J =10.1&2.5 Hz)

TABLE 13 Elementary analysis Catalyst (wt %) component C H Zr ¹H-NMRspectral data (δ:ppm) (a)-64 61.03 4.94 19.21 δ 2.02(s, 6H), 5.88(s,10H), 6.39(dd, 2H, J = 8.6&4.9Hz), 6.82-6.89 (m, 4H) (a)-65 70.76 4.8917.77 δ 5.97(s, 10H), 6.72(dd, 2H, J = 6.8&1.6Hz), 7.35-7.46(m, 8H),7.80(d, 2H, J = 8.0Hz), 8.53(d, 2H, J = 8.0Hz) (a)-66 70.62 5.01 17.68 δ6.01(s, 10H), 7.10(dd, 2H, J = 8.8&2.3Hz), 7.21(d, 2H, J = 2.3 Hz),7.23(ddd, 2H, J = 8.0, 6.8& 1.2Hz), 7.35(ddd, 2H, J = 8.0, 6.8& 1.2Hz),7.70(d, 2H, J = 8.8Hz), 7.74(d, 2H, J = 8.0Hz), 7.75(d, 2H, J = 8.0Hz)(a)-67 55.32 4.02 18.96 δ 5.95(s, 10H), 6.59(dddd, 2H, J = 7.8, 7.2,4.5&1.8Hz), 6.79-6.91(m, 4H), 6.95(t, 2H, J = 8.2Hz) (a)-68 51.86 3.8417.63 δ 5.91(s, 10H), 6.52(td, 2H, J = 7.7, 7.7&1.7Hz), 6.58(td, 2H, J =7.7, 7.7&1.4Hz)6.79(dd, 2H, J = 7.7&1.7Hz), 7.31(dd, 2H, J = J =7.7&1.4Hz)

EXAMPLE 69 Synthesis of Catalyst Component (b)-1(Bis(methylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium)

The reaction was carried out under the same condition as in Example 1except that 58.2 mg of ²-trifluoremethylphenol were added to 10 ml oftoluene solution containing 53.9 mg of bis(methylcyclopentadienyl)dimethyl zirconium. After the completion of the reaction, toluene wasdistilled off under reduced pressure to yield a white solid (catalystcomponent (b)-1). The yield amount of the catalyst component (b)-1 was109.7 mg corresponding to 99% yield.

The resulting product was confirmed as the final transition metalcompound by means of ¹H-NMR spectroscopy and the elementary analysis.The results were as follows:

¹H-NMR spectral data: δ 1.91 (s, 6H), 5.85 (t, 4H, J=2.3 Hz), 5.87(t,4H, J=2.3 Hz), 6.59(t, 2H, J=7.8 Hz), 6.77(d, 2H, J=7.8 Hz), 7.09 (dt,2H, J=7.8 and 1.5 Hz),7.48 (dd, 2H, J=7.8 and 1.5 Hz), elementaryanalysis: C 54.53, H 4.17, Zr 15.72

EXAMPLES 70 TO 74 Synthesis of Catalyst Components (b)-2 to (b)-6

The transition metal compounds were synthesized in the same manner as inExample 69 except that 2-trifluoromethylphenol to be reacted withbis(methylcyclopentadienyl)dimethyl zirconium was exchanged by thesubstituted phenol compounds as shown in Table 14 and the amount of eachstarting material was shown in Table 14 (Catalyst components are (b)-2to (b)-6). The yield amount, yield and appearance of each catalystcomponent were summarized in Table 14 and the results of the elementaryanalysis and ¹H-NMR spectral data in Table 15.

TABLE 14 (MeCp)₂ZrMe₂ Yield Example Catalyst (used amount) SubstitutedUsage amount Yield No. component (mg) phenol compound (mg) (mg) (%)Appearance Ex. 69 (b)-1 53.9 2-trifluoromethylphenol 58.2 109.7  99white solid Ex. 70 (b)-2 55.0 3-trifluoromethylphenol 58.7 113.7 100colorless oil Ex. 71 (b)-3 56.3 4-trifluoromethylphenol 60.5 115.4 100colorless oil Ex. 72 (b)-4 58.7 2-tert-butylphenol 62.9 117.4 100colorless oil Ex. 73 (b)-5 59.3 3-tert-butylphenol 63.6 119.4 100colorless oil Ex. 74 (b)-6 71.2 4-tert-butvlphenol 76.5 144.5 100 yellowoil

TABLE 15 Elementary analysis Catalyst (wt %) component C H Zr ¹H-NMRspectral data (δ:ppm) (b)-1 54.53 4.17 15.72 δ 1.91(s, 6H), 5.85(t, 4H,J = 2.3Hz), 5.87(t, 4H, J = 2.3Hz), 6.59(t, 2H, J = 7.8Hz), 6.77(d, 2H,J = 7.8Hz), 7.09(dt, 2H, J = 7.8, 7.8&1.5Hz), 7.48(dd, 2H, J =7.8&1.5Hz) (b)-2 54.48 4.07 15.79 δ 1.94(s, 6H), 5.87(t, 4H, J = 2.8Hz),5.91(t, 4H, J = 2.8Hz), 7.02(t, 2H, J = 7.8Hz), 7.05-7.09(m, 4H), 7.18(s, 2H) (b)-3 54.43 4.01 15.77 δ 1.78(s, 6H), 5.64(t, 4H, J = 2.6Hz),5.70(t, 4H, J = 2.6Hz), 6.52(d, 4H, J = 8.3Hz), 7.49(d, 4H, J = 8.3Hz)(b)-4 70.16 7.69 16.44 δ 1.54(s, 18H), 1.93(s, 6H), 5.95(t, 4H, J =2.6Hz), 6.00(t, 4H, J = 2.6 Hz), 6.63(dd, 2H, J = 7.7&1.3Hz), 6.92(dt,2H, J = 7.7, 7.7&1.3Hz), 7.15(dt, 2H, J = 7.7, 7.7&1.7Hz), 7.38(dd, 2H,J = 7.7&1.7Hz) (b)-5 69.99 7.81 16.52 δ 1.35(s, 18H), 2.00(s, 6H),5.86(t, 4H, J = 2.5Hz), 5.90(t, 4H, J = 2.5 Hz), 6.70(ddd, 2H, J = 7.9,2.1&1.0 Hz), 6.96(ddd, 2H, J = 7.9, 2.1&1.0 Hz), 7.05(t, 2H, J = 2.1Hz),7.26(t, 2H, J = 7.9Hz) (b)-6 70.02 7.35 16.62 δ 1.33(s, 18H), 1.98(s,6H), 5.84(t, 4H, J = 2.5Hz), 5.90(t, 4H, J = 2.5 Hz), 6.85(d, 4H, J =8.7Hz), 7.33(d, 4H, J = 8.7Hz)

EXAMPLE 75 Synthesis of Catalyst Component (c)-1(Bis(n-butylcyclopentadienyl)bis(2-fluorophenoxy)zirconium)

The same reaction as well as treatment after the reaction was carriedout as in Example 1 except that 69.8 mg of 2-fluorophenol was added to10 ml of toluene solution containing 106.6 mg ofbis(n-butylcyclopentadienyl)dimethyl zirconium and reacted. 162.9 mg ofcolorless oil product (catalyst component (c)-1) was obtained; yield:100%. The resulting product was confirmed as the final transition metalcompound by means of ¹H-NMR spectroscopy and the elementary analysis.The results are as follows:

¹H-NMR spectral data: δ 0.77 (t, 6H, J=7.3 Hz), 1.13 (sext, 4H, J=7.5Hz), 1.35 (quint, 4H, J=7.8 Hz), 2.43 (t, 4H, J=7.8 Hz), 5.94 (t, 4H,J=2.6 Hz),5.97(t, 4H, J=2.6), 6.60 (dddd, 2H, J=7.8, 7.2, 4.5 and 1.8Hz), 6.92 (tdd, 2H, J=7.8, 7.8, 1.5 and 0.5 Hz), 6.99 (dt, 2H, J=7.8,7.8, and.1.8 Hz), 7.03 (ddd, 2H, J=11.4, 8.0, and 1.6 Hz), elementaryanalysis: C 64.76, H 6.18, Zr 16.39.

EXAMPLES 76 TO 83 Synthesis of Catalyst Components (c)-2 to (c)-9

The catalyst components were synthesized in the same manner as inExample 75 except that 2-fluorophenol to be reacted withbis(n-butylcyclopentadienyl)dimethyl zirconium was exchanged by thesubstituted phenol compounds as shown in Table 16 and 17 and the amountof each starting material was shown in Tables 16 and 17. The yieldamount, yield and appearance of each catalyst component were summarizedin Tables 16 and 17 and the results of ¹H-NMR spectral data and theelementary analysis in Tables 18 and 19.

TABLE 16 (nBuCp)₂ZrMe₂ Yield Example Catalyst (used amount) SubstitutedUsage amount Yield No. component (mg) phenol compound (mg) (mg) (%)Appearance Ex. 75 (c)-1 106.6 2-fluorophenol 69.8 162.9 100 colorlessoil Ex. 76 (c)-2 97.5 3-fluorophenol 69.1 150.4 100 colorless oil Ex. 77(c)-3 101.7 4-fluorophenol 79.3 156.1 100 colorless oil Ex. 78 (c)-476.5 2-trifluoromethylphenol 67.3 138.2  99 colorless oil Ex. 79 (c)-588.2 3-trifluoromethylphenol 78.9 159.8 100 colorless oil Ex. 80 (c)-680.3 4-trifluoromethylphenol 71.7 146.4 100 colorless oil

TABLE 17 (nBuCp)₂ZrMe₂ Yield Example Catalyst (used amount) SubstitutedUsage amount Yield No. component (mg) phenol compound (mg) (mg) (%)Appearance Ex. 81 (c)-7 70.0 2-tert-butylphenol 57.4 125.4 100 colorlessoil Ex. 82 (c)-8 74.7 3-tert-butylphenol 61.6 133.3 100 colorless oilEx. 83 (c)-9 72.9 4-tert-butylphenol 59.0 130.5 100 colorless oil

TABLE 18 Elementary analysis Catalyst (wt %) component C H Zr ¹H-NMRspectral data (δ:ppm) (c)-1 64.76 6.18 16.39 δ 0.77(t, 6H, J = 7.3Hz),1.13(sext, 4H, J = 7.5Hz), 1.35(quint, 4H, J = 7.8Hz), 2.43(t, 4H, J =7.8Hz), 5.94(t, 4H, J = 2.6Hz), 5.97(t, 4H, J = 2.6Hz), 6.60(dddd, 2H, J= 7.8, 7.2, 4.5&1.8Hz), 6.92(tdd, 2H, J = 7.8, 7.8, 1.5&0.5Hz), 6.99(dt,2H, J = 7.8, 7.8&1.8Hz), 7.03(ddd, 2H, J = 11.4, 8.0&1.6Hz) (c)-2 64.716.34 15.99 δ 0.77(t, 6H, J = 7.3Hz), 1.12(sext, 4H, J = 7.5Hz),1.31(quint, 4H, J = 7.8Hz), 2.31(t, 4H, J = 7.8Hz), 5.80 (t, 8H, J =1.6Hz), 6.52(ddd, 2H, J = 8.2, 2.1&0.8Hz), 6.55-6.61(m, 4H), 6.98(dt,2H, J = 8.2, 8.2&7.4Hz) (c)-3 64.41 6.44 16.84 δ 0.79(t, 6H, J = 7.5Hz),1.16(sext, 4H, J = 7.5Hz), 1.35(quint, 4H, J = 7.5Hz), 2.35(t, 4H, J =7.5Hz), 5.85(s, 8H), 6.55(dd, 4H, J = 8.7& 4.5Hz), 6.90(t, 4H, J =8.7Hz)

TABLE 19 Elementary analysis Catalyst (wt %) component C H Zr ¹H-NMRspectral data (δ:ppm) (c)-4 58.40 5.51 13.46 δ 0.74(t, 6H, J = 7.3Hz),1.10(sext, 4H, J = 7.5Hz), 1.30(quint, 4H, J = 7.6Hz), 2.44(t, 4H, J =7.6Hz), 5.96 (t, 4H, J = 2.6Hz), 6.00(t, 4H, J = 2.6 Hz), 6.59(t, 2H, J= 7.6Hz), 6.83 (d, 2H, J = 8.1Hz), 7.12(ddd, 2H, J = 8.1, 7.6&1.5Hz),7.49(dd, 2H, J = 7.6&1.5Hz) (c)-5 58.84 5.36 13.74 δ 0.77(t, 6H, J =7.3Hz), 1.11(sext, 4H, J = 7.5Hz), 1.28(quint, 4H, J = 7.8Hz), 2.27(t,4H, J = 7.8Hz), 5.75- 5.79(m, 8H), 6.78(m, 2H, J = 7.7Hz), 7.01-7.08(m,4H) (c)-6 58.42 5.61 13.79 δ 0.77(t, 6H, J = 7.3Hz), 1.11(sext, 4H, J =7.5Hz), 1.27(quint, 4H, J = 7.7Hz), 2.26(t, 4H, J = 7.7Hz), 5.78 (t, 4H,J = 2.2Hz), 5.78(t, 4H, J = 2.2 Hz), 6.58(d, 4H, J = 8.5Hz), 7.50 (d,4H, J = 8.5Hz) (c)-7 72.40 8.15 14.30 δ 0.74(t, 6H, J = 7.3Hz),1.09(sext, 4H, J = 7.5Hz), 1.28(quint, 4H, J = 7.6Hz), 1.57(s, 18H),2.47(t, 4H, J = 7.6Hz), 6.03(t, 4H, J = 2.6Hz), 6.13 (t,4H, J = 2.6Hz),6.68(dd, 2H, J = 7.6&1.2Hz), 6.91(dt, 2H, J = 7.6, 7.6 &1.2Hz), 7.17(dt,2H, J = 7.6, 7.6& 1.7Hz), 7.38(dd, 2H, J = 7.6&1.7Hz) (c)-8 71.99 8.5414.59 δ 0.80(t, 6H, J = 7.3Hz), 1.18(sext, 4H, J = 7.5Hz), 1.36(s, 18H),1.41 (quint, 4H, J = 7.8Hz), 2.48(t, 4H, J = 7.8Hz), 5.98(s, 8H),6.37(ddd, 2H, J = 7.9, 2.1&0.8Hz), 6.96(ddd, 2H, J = 7.9, 2.1&0.8Hz),7.05(t, 2H, J = 2.1Hz), 7.27(t, 2H, J = 7.9Hz) (c)-9 72.17 8.44 14.38 δ0.79(t, 6H, J = 7.3Hz), 1.17(sext, 4H, J = 7.5Hz), 1.32(s, 18H), 1.38(quint, 4H, J = 7.8Hz), 2.47(t, 4H, J = 7.8Hz), 5.96(s, 8H), 6.88(d, 4H,J = 8.6Hz), 7.34(d, 4H, J = 8.6Hz)

EXAMPLE 84 Synthesis of Catalyst Component(d)-1(Bis(1,3-dimethylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium

The reaction was carried out under the same condition as in Example 1except that 62.5 mg of 2-trifluoromethylphenol were added to 10 ml oftoluene solution containing 59.3 mg ofbis(1,3-dimethylcyclopentadienyl)dimethyl zirconium. The product wasrecrystallized from toluene to yield the transition metal compound aswhite crystal (catalyst component (d)-1). The yield amount was 63.1 mgcorresponding to 53% yield.

The resulting product was confirmed as the final transition metalcompound by means of ¹H-NMR spectroscopy and the elementary analysis.The results are shown as follows:

¹H-NMR spectral data: δ 1.95 (s, 12H), 5.72 (t, 2H, J=2.4 Hz), 5.77 (d,4H, J=2.4 Hz), 6.58 (t, 2H, J=7.8 Hz), 6.78(d, 2H, J=7.8 Hz), 7.06 (t,2H, J=7.8 Hz), 7.49 (dd, 2H, J=7.8, and 1.6 Hz), elementary analysis : C55.82, H 4.63, Zr 15.09.

EXAMPLES 85 TO 89 Synthesis of Catalyst Components (d)-2 to (d)-6

The reaction was carried out in the same manner as in Example 84 exceptthat 2-trifluoromethylphenol to be reacted withbis(1,3-dimethylcyclopentadienyl)dimethyl zirconium was exchanged by thesubstituted phenol compounds as shown in Table 20 and the amount of eachstarting material was shown in Table 20. The yield amount, yield andappearance of each catalyst component were summarized in Table 20 andthe results of elementary analysis and ¹H-NMR spectral data in Table 21.

TABLE 20 (MeCp)₂ZrMe₂ Yield Example Catalyst (used amount) SubstitutedUsage amount Yield No. component (mg) phenol compound (mg) (mg) (%)Appearance Ex. 84 (d)-1 59.3 2-trifluoromethylphenol 62.5 63.1  53 whitecrystal Ex. 85 (d)-2 55.9 3-trifluoromethylphenol 58.9 110.7 100 yellowoil Ex. 86 (d)-3 59.9 4-trifluoromethylphenol 63.3 115.8  99 colorlessoil Ex. 87 (d)-4 53.6 2-tert-butylphenol 52.4 102.5 100 white solid Ex.88 (d)-5 51.1 3-tert-butylphenol 50.4 96.9 100 colorless oil Ex. 89(d)-6 59.5 4-tert-butylphenol 58.1 114.9 100 white solid

TABLE 21 Elementary analysis Catalyst (wt %) component C H Zr ¹H-NMRspectral data (δ:ppm) (d)-1 55.82 4.63 15.09 δ 1.95(s, 12H), 5.72(t, 2H,J = 2.4Hz), 5.77(d, 4H, J = 2.4Hz), 6.58 (t, 2H, J = 7.8Hz), 6.78(d, 2H,J = 7.8Hz), 7.06(t, 2H, J = 7.8Hz), 7.49 (dd, 2H, J = 7.8&1.6Hz) (d)-255.97 4.56 15.13 δ 1.78(s, 12H), 5.51(d, 4H, J = 2.4Hz), 5.57(t, 2H, J =2.4Hz), 6.77 (d, 2H, J = 7.8Hz), 7.00(t, 2H, J = 7.8Hz), 7.05(t, 2H, J =7.8Hz) (d)-3 56.17 4.27 15.25 δ 1.78(s, 12H), 5.53(d, 2H, J = 2.5Hz),5.58(t, 4H, J = 2.5Hz), 6.56 (d, 4H, J = 8.4Hz), 7.45(d, 4H, J = 8.4Hz)(d)-4 71.01 7.78 15.86 δ 1.54(s, 18H), 1.96(s, 12H), 5.86(d, 4H, J =2.4Hz), 6.03(t, 2H, J = 2.4 Hz), 6.71(dd, 2H, J = 7.7&1.2Hz), 6.93(dt,2H, J = 7.7, 7.7&1.2Hz), 7.19(dt, 2H, J = 7.7, 7.7&1.8Hz), 7.38(dt, 2H,J = 7.7, 7.7&1.8Hz) (d)-5 70.72 8.04 15.67 δ 1.32(s, 18H), 2.00(s, 12H),5.70(d, 4H, J = 2.4Hz), 5.84(t, 2H, J = 2.4 Hz), 6.74(ddd, 2H, J = 7.8,2.1& 0.8Hz), 6.93(ddd, 2H, J = 7.8, 2.1& 0.8Hz), 7.02(t, 2H, J = 2.1Hz),7.23 (t, 2H, J = 7.8Hz) (d)-6 70.75 7.82 15.43 δ 1.31(s, 18H), 1.98(s,12H), 5.68(d, 4H, J = 2.4Hz), 5.82(t, 2H, J = 2.4 Hz), 6.86(d, 4H, J =8.6Hz), 7.29(d, 4H, J = 8.6Hz)

EXAMPLE 90 Synthesis of Catalyst Component (e)-1(Bis(pentamethylcyclopentadienyl)bis(2-fluorophenoxy)zirconium)

The reaction was carried out in the same condition as in Example 1except that 123.3 mg of 2-fluorophenol were added to 10 ml of toluenesolution containing 237.7 mg of bis(pentamethylcyclopentadienyl)dimethylzirconium and reacted. The product was recrystallized from toluene toyield the transition metal compound as white crystal (catalyst component(e)-1). The yield amount was 210.7 mg corresponding to 66% yield.

The result of ¹H-NMR spectroscopy and the elementary analysis of productare summarized as follows:

¹H-NMR spectral data: δ 1.85 (s, 30H), 6.59 (dddd, 2H, J =7.5, 7.2, 4.4and 1.6 Hz), 6.96(dddd, 2H, J=8.4, 7.2, 1.6 and 0.7 Hz), 7.03 (ddd, 2H,J=11.8, 7.5 and 1.6 Hz), 7.19(d, 2H, J=8.4 Hz), elementary analysis: C65.71, H 6.77, Zr 15.71

EXAMPLE 91 TO 92 Synthesis of Catalyst Components (e)-2 and (e)-3

The catalyst components were synthesized in the same manner as inExample 90 except that 2-fluorophenol to be reacted withbis(pentamethylcyclopentadienyl)dimethyl zirconium was exchanged by thesubstituted phenol compounds as shown in Table 22 and the amount of eachstarting material was shown in Table 22. The yield amount, yield andappearance of each catalyst component were summarized in Table 22 andthe results of elementary analysis and ¹H-NMR spectroscopy in Table 23.

TABLE 22 (MeCp)₂ZrMe₂ Yield Example Catalyst (used amount) SubstitutedUsage amount Yield No. component (mg) phenol compound (mg) (mg) (%)Appearance Ex. 90 (e)-1 237.7 2-fluorophenol 123.3 210.7 66 whitecrystal Ex. 91 (e)-2 220.2 3-fluorophenol 114.1 52.6 18 white crystalEx. 92 (e)-3 245.7 4-fluorophenol 127.3 183.6 55 white crystal

TABLE 23 Elementary analysis Catalyst (wt %) component C H Zr ¹H-NMRspectral data (δ:ppm) (e)-1 65.71 6.77 15.71 δ 1.85(s, 30H), 6.59(dddd,2H, J = 7.5, 7.2, 4.4&1.6Hz), 6.96(dddd, 2H, J = 8.4, 7.2, 1.6&0.7Hz),7.03 (ddd, 2H, J = 11.8, 7.5&1.6Hz), 7.19(d, 2H, J = 8.4Hz) (e)-2 65.496.72 15.46 δ 1.74(s, 30H), 6.54(tdd, 2H, J = 8.2, 8.2, 2.3&0.8Hz),6.64(ddd, 2H, J = 8.2, 2.3&0.8Hz), 6.99(dt, 2H, J = 11.5, 2.3&2.3Hz),6.99(td, 2H, J = 8.2, 8.2&7.5Hz) (e)-3 65.42 7.04 15.22 δ 1.79(s, 30H),6.64(dd, 4H, J = 9.0 &4.5Hz), 6.89(dd, 4H, J = 9.0& 8.4Hz)

EXAMPLE 93 Synthesis of Catalyst Component (f)-1(Ethylenebis(indenyl)bis(2-trifluoromethylphenoxy)zirconium)

The same reaction as well as treatment after the reaction was carriedout as in Example 1 except that 60.4 mg of 2-trifluoromethylphenol wereadded to 10 ml of toluene solution containing 70.3 mg ofethylenebis(indenyl)dimethyl zirconium. 124.5 mg of colorless oilyproduct were obtained in a yield of 100%.

The results of ¹H-NMR spectroscopy and the elementary analysis of theproduct are shown as follows:

¹H-NMR spectral data: δ 2.60-2.85 (m, 4H), 5.63 (d, 2H, J=3.2 Hz), 6.40(d, 2H, J=3.2 Hz), 6.57 (t, 2H, J=7.8 Hz), 6.79 (d, 2H, J=7.8 Hz), 6.90(dd, 4H, J=6.5 and 3.3 Hz), 7.09 (dt, 2H, J=7.8, 7.8 and 1.6 Hz), 7.24(dd, 4H, J=6.5, and 3.3 Hz), 7.52 (dd, 2H, J=7.8 and 1.6 Hz), elementaryanalysis: C 60.82, H 3.92, Zr 13.41.

EXAMPLES 94 TO 95 Synthesis of Catalyst Components (f)-2 and (f)-3

The catalyst components were synthesized in the same manner as inExample 93 except that 2-trifluoromethylphenol to be reacted withethylenebis(indenyl)dimethyl zirconium was exchanged by the substitutedphenol compounds as shown in Table 24 and the amount of each startingmaterial was shown in Table 24. The yield amount, yield and appearanceof each catalyst component are summarized in Table 24 and the results ofelementary analysis and ¹H-NMR spectroscopy in Table 25.

TABLE 24 Et(Ind)₂ZrMe₂ Yield Example Catalyst (used amount) SubstitutedUsage amount Yield No. component (mg) phenol compound (mg) (mg) (%)Appearance Ex. 93 (f)-1 70.3 2-trifluoromethylphenol 60.4 124.5 100 colorless oil Ex. 94 (f)-2 65.9 3-trifluoromethylphenol 56.6 42.5 36white crystal Ex. 95 (f)-3 72.5 4-trifluoromethylphenol 62.2 126.8 99white solid

TABLE 25 Elementary analysis Catalyst (wt %) component C H Zr ¹H-NMRspectral data (δ:ppm) (f)-1 60.82 3.92 13.41 δ 2.60-2.85(m, 4H), 5.63(d,2H, J = 3.2Hz), 6.40(d, 2H, J = 3.2Hz), 6.57 (t, 2H, J = 7.8Hz), 6.79(d,2H, J = 7.8Hz), 6.90(dd, 4H, J = 6.5&3.3 Hz), 7.09(dt, 2H, J = 7.8,7.8&1.6 Hz), 7.24(dd, 4H, J = 6.5&3.3Hz), 7.52(dd, 2H, J = 7.8&1.6Hz)(f)-2 60.90 3.76 13.47 δ 2.58-2.86(m, 4H), 5.67(d, 2H, J = 3.4Hz),6.41(d, 2H, J = 3.4Hz), 6.80 (d, 2H, J = 7.7Hz), 6.91(dd, 4H, J =6.5&3.3Hz), 7.01(t, 2H, J = 7.7Hz), 7.06(t, 2H, J = 7.7Hz), 7.14(s, 2H),7.21(dd, 4H, J = 6.5&3.3Hz) (f)-3 60.73 3.86 13.39 δ 2.61-2.79(m, 4H),5.65(d, 2H, J = 3.3Hz), 6.41(d, 2H, J = 3.3Hz), 6.59 (d, 4H, J = 8.5Hz),6.91(dd, 4H, J = 6.4&3.4Hz), 7.22(dd, 4H, J = 6.4& 3.4Hz), 7.43(d, 4H, J= 8.5Hz)

II. Polymerization and Copolymerization EXAMPLE 96

To a 800 ml autoclave having been dried sufficiently and exchanged byethylene, 5 ml of toluene solution containing 0.05 μmol of catalystcomponent (a)-1 and 0.9 ml of toluene solution of methylaluminoxane(aluminum content 1.5 mmol) manufactured by Tosoaczo Co. (Trade name:MMAO) were introduced with 300 ml of toluene. The inner temperature ofthe autoclave was raised at 70° C., and ethylene gas was introduced upto 0.3 MPa. Polymerization was carried out for 1 hr while keeping thepressure. After discharging ethylene, a small amount of isopropylalcohol was added to terminate the polymerization. The resulting polymerwas isolated and dried to yield 12.1 g of polymer. The activity per unitzirconium was 2640 kg polymer/g Zr.

COMPARATIVE EXAMPLE 1 (1)Synthesis of Catalyst Component (r)-1(Dicyclopentadienyldiphenoxy zirconium)

The reaction of dicyclopentadienyldimethyl zirconium and phenol wascarried out in the same manner as in Example 1 except that phenol wasused instead of orthocresol. A product of white solid was obtained(catalyst component (r)-1). The product was confirmed as thedicyclopentadienyldiphenoxy zirconium by means of ¹H-NMR spectroscopy.

(2) Polymerization:

The polymerization of ethylene was carried out in the same manner as inExample 96 except that 5 ml of toluene solution containing 0.05 μmol ofthe product obtained in the above (1) instead of catalyst component(a)-1 was used. As a result, 5.2 g of polymer were obtained and theactivity per unit zirconium was 1140 kg polymer/g Zr. It is clear thatthe activity of this is lower than that of the transition metal compoundof Example 1 having the same cyclopentadienyl ligand portion.

COMPARATIVE EXAMPLE 2 (1) Synthesis of Catalyst Component (r)-2(Dicyclopentadienyldithiophenoxy zirconium)

The reaction of dicyclopentadienyldimethyl zirconium and thiophenol wascarried out in the same manner as in Example 1 that thiophenol was usedinstead of orthocresol. A product of pale yellow solid was obtained.

(2) Polymerization

The polymerization of ethylene was carried out in the same manner as inExample 96 except that 5 ml of toluene solution containing 0.05 μmol ofthe product obtained in the above (1) instead of catalyst component(a)-1 was used. As a result, 4.0 g of polymer was obtained and theactivity per unit zirconium was 880 kg polymer/g Zr. It is clear thatthe activity of this catalyst component (r)-2 is lower than that of thetransition metal compound of Example 67 having the same cyclopentadienylligand portion.

EXAMPLES 97-135

The polymerization of ethylene was carried out in the same manner as inExample 96 except that the catalyst components produced in Examples 2-68respectively were used instead of the catalyst component (a)-1. Theresults are summarized in Tables 26 to 28.

TABLE 26 Catalyst activity Catalyst Usage polymer yield (kg polymer/Example No. component (μmol) (g) g Zr) Comparative (r)-1 0.05 5.2 1140Example 1 Example 96 (a)-1 0.05 12.1 2640 Example 97 (a)-3 0.05 7.6 1650Example 98 (a)-6 0.05 8.0 1740 Example 99 (a)-7 0.05 13.5 2950 Example100 (a)-9 0.05 9.3 2050 Example 101 (a)-11 0.05 13.6 2990 Example 102(a)-12 0.05 9.2 2020 Example 103 (a)-15 0.05 7.6 1660 Example 104 (a)-160.05 12.0 2630 Example 105 (a)-17 0.05 10.5 2310 Example 106 (a)-19 0.059.0 1970 Example 107 (a)-23 0.05 10.1 2210 Example 108 (a)-24 0.05 10.62330 Example 109 (a)-25 0.05 11.4 2500 Example 110 (a)-26 0.05 10.1 2210Example 111 (a)-27 0.05 10.2 2230

TABLE 27 Catalyst activity Catalyst Usage polymer yield (kg polymer/Example No. component (μmol) (g) g Zr) Example 112 (a)-28 0.05 13.1 2860Example 113 (a)-30 0.05 11.7 2570 Example 114 (a)-32 0.05 8.4 1840Example 115 (a)-34 0.05 13.1 2890 Example 116 (a)-35 0.05 9.1 1980Example 117 (a)-3W 0.05 11.1 2440 Example 118 (a)-39 0.05 9.7 2120Example 119 (a)-42 0.05 8.8 1930 Example 120 (a)-43 0.05 9.6 2100Example 121 (a)-46 0.05 8.7 1900 Example 122 (a)-47 0.05 8.0 1750Example 123 (a)-48 0.05 7.8 1720 Example 124 (a)-49 0.05 10.9 2380Example 125 (a)-54 0.05 7.7 1690 Example 126 (a)-57 0.05 8.1 1780Example 127 (a)-58 0.05 10.9 2380 Example 128 (a)-59 0.05 14.2 3110

TABLE 28 Catalyst activity Catalyst Usage polymer yield (kg polymer/Example No. component (μmol) (g) g Zr) Eample 129 (a)-60 0.05 11.3 2480Example 130 (a)-61 0.05 12.1 2640 Example 131 (a)-62 0.05 11.4 2500Example 132 (a)-64 0.05 15.8 3460 Example 133 (a)-65 0.05 9.6 2110Comparative (r)-2 0.05 4.0 880 Example 2 Example 134 (a)-67 0.05 6.71470 Example 135 (a)-68 0.05 7.8 1700

EXAMPLES 136-162

The polymerization of ethylene was carried out in the same manner as inExample 96 except that instead of catalyst component (a)-1 the catalystcomponents ((b)-1 to (b)-6, (c)-1 to (c)-9 and (d)-1 to (d)-6) and theamount of catalyst component as shown in Tables 29 and 30 were used. Theresults are summarized in Tables 29 and 30.

COMPARISON EXAMPLE 3 (1) Synthesis of Catalyst Component (r)-3(Bis(methylcyclopentadienyl)diphenoxy zirconium)

The reaction of bis(methylcyclopentadienyl)dimethyl zirconium and phenolwas carried out in the same manner as in Example 69 except that phenolwas used instead of 2-trifluoromethylphenol; A product of white crystalwas obtained.

(2) Polymerization

The polymerization of ethylene was carried out in the same manner as inExample 96 except that 5 ml of toluene solution containing ^(0.05) μmolof the product obtained in the above (1) was used instead of thecatalyst component (a)-1. The results are shown in Table 29. Theactivity of the catalyst component (r)-3 is lower than that of thetransition metal compounds having the same cyclopentadienyl ligandportion, as shown, respectively in examples.

COMPARATIVE EXAMPLE 4 (1) Synthesis of Catalyst Component (r)-4(Bis(n-butylcyclopentadienyl)diphenoxy Zirconium)

The reaction of bis(n-butylcyclopentadienyl)dimethyl zirconium andphenol was carried out in the same manner as in Example 75 except thatphenol was used instead of 2-fluorophenol; A colorless oil product wasobtained.

(2) Polymerization

The polymerization of ethylene was carried out in the same manner as inExample 96 except that 5 ml of toluene solution containing 0.03 μmol ofthe product obtained in the above (1) was used instead of the catalystcomponent (a)-1; The results as shown in Table 30 were obtained. Theactivity of the catalyst component (r)-4 is lower than that of thetransition metal compounds having the same cyclopentadienyl ligandportion as shown, respectively, in examples.

COMPARATIVE EXAMPLE 5 (1) Synthesis of Catalyst Component (r)-5(Bis(1,3-dimethylcyclopentadienyl)diphenoxy zirconium)

The reaction of bis (1,3-dimethylcyclopentadienyl) dimethyl zirconiumand phenol was carried out in the same manner as in Example 84 exceptthat phenol was used instead of 2-trifluoromethylphenol; A product ofwhite solid was obtained.

(2) Polymerization

The polymerization of ethylene was carried out in the same manner as inExample 96 except that 5 ml of toluene solution containing 0.03 μmol ofthe product obtained in the above (1) instead of catalyst component(a)-1 was used; The results as shown in Table 30 were obtained. Theactivity of the catalyst component (r)-5 is lower than that of thetransition metal compounds having the same cyclopentadienyl ligandportion, as shown, respectively in examples.

TABLE 29 Catalyst activity Catalyst Usage polymer yield (kg polymer/Example No. component (μmol) (g) g Zr) Example 136 (b)-1 0.05 8.7 1910Example 137 (b)-2 0.05 9.7 2120 Example 138 (b)-3 0.05 7.8 1700 Example139 (b)-4 0.05 14.9 3270 Example 140 (b)-5 0.05 16.4 3600 Example 141(b)-6 0.05 11.1 2440 Comparative (r)-3 0.05 5.0 1110 Example 3

TABLE 30 Catalyst activity Catalyst Usage polymer yield (kg polymer/Example No. component (μmol) (g) g Zr) Example 142 (c)-1 0.03 15.8 5760Example 143 (c)-2 0.03 18.0 6560 Example 144 (c)-3 0.03 16.1 5870Example 145 (c)-4 0.03 19.7 7190 Example 146 (c)-5 0.03 19.2 7020Example 147 (c)-6 0.03 14.5 5300 Example 148 (c)-7 0.03 8.8 3220 Example149 (c)-8 0.03 17.1 6240 Example 150 (c)-9 0.03 14.9 5450 Comparative(r)-4 0.03 10.1 3680 Example 4 Example 151 (d)-1 0.03 8.6 3140 Example152 (d)-2 0.03 7.1 2580 Example 153 (d)-3 0.03 8.0 2940 Example 154(d)-4 0.03 9.4 3440 Example 155 (d)-5 0.03 8.3 3020 Example 156 (d)-60.03 8.0 2920 Comparative (r)-5 0.03 5.4 1980 Example 5

EXAMPLE 157 Copolymerization of Ethylene and 1-Hexene

Ethylene was polymerized while being introduced continuously in the samemanner as in Example 96 except that 300 ml of toluene and 10 ml of1-hexene were fed to an autoclave and 5 ml of toluene solutioncontaining 0.1 μmol of the catalyst component (a)-19 was used. Afterdischarging ethylene, a small amount of isopropyl alcohol was added toterminate the polymerization. The resulting polymer was isolated anddried to yield 13.9 g of polymer. The activity per unit zirconium was1,520 kg polymer/g Zr. It was confirmed that the polymer was thecopolymer of ethylene and 1-hexene by means of ¹³C-NMR spectroscopy. Thecomonomer content in the polymer was 1.13 mol%.

EXAMPLE 158 Copolymerization of Ethylene and 1-Hexene

300 ml of toluene and 6.7 ml of 1-hexene were fed to an autoclave, 0.25mmol of triisobutyl aluminum, 0.1 μmol of the catalyst component (a)-7and 2.0 μmol of triphenylmethyltetrakis(pentafluorophenyl)borate wereadded in order, the mixture was heated to 70° C. and polymerization wascarried out for 1 hr while feeding ethylene continuously in such amanner that the partial pressure of ethylene was 0.3 MPa. The polymerwas isolated and dried to yield 13.1 g of polymer. The activity per unitzirconium was 1,430 kg polymer/g Zr. The content of 1-hexene in thepolymer was determined as 1.33 mol %.

EXAMPLE 159 Copolymerization of Ethylene and 1, 9-Decadiene

The polymerization was carried out while feeding ethylene in the samemanner as in Example 96 except that 300 ml of toluene and 11.0 g of 1,9-decadiene were fed to an autoclave and 0.1 μmol of the catalystcomponent (a)-7 was added. The resulting polymer was subjected to thepost-treatment to yield 11.6 g of polymer. The activity per unitzirconium was 1,260 kg polymer/g Zr. It was confirmed that the polymerwas the copolymer of ethylene and 1, 9-decadiene from ¹H-NMR spectraldata, and the comonomer content in the polymer was 1.02 mol %.

EXAMPLE 160 Copolymer of Ethylene and 2-Norbornene

90 ml of toluene and 10 ml (30 mmol) of 2-norbornene were added to anautoclave and then 3.7 ml of toluene solution of methylalminoxane(corresponding to 6.0 mmol of aluminum) and 1 ml of toluene solutioncontaining 1 μmol of the catalyst component (d)-3 were added. The innertemperature of autoclave was kept at 60° C., ethylene gas was introducedup to 0.3 MPa and the mixture was polymerized for 30 min while keepingthe pressure. The resulting polymer solution was diluted with toluene,then treated with aq.0.6N-HCl solution and water, then, added with alarge amount of methanol to separate the polymer. After filtrating anddrying the polymer, 3.13 g of polymer was obtained and the activity perunit zirconium was 34.3 kg polymer/g Zr. It was confirmed that thepolymer was the copolymer of ethylene and 2-norbornene from ¹³H-NMRspectral data. The content of 2-norbornene in the polymer was 13.4 mol%.

EXAMPLE 161-163

The copolymerization of ethylene and 2-norbornene was carried out in thesame manner as in Example 160 except that catalyst components(f)-1-(f)-3 were used instead of the catalyst component (d)-3. Theresults are summarized in Table 31.

COMPARATIVE EXAMPLE 6 (1) Synthesis of Catalyst Component (r)-6(Ethylenebis(indenyl)diphenoxy zirconium)

The reaction of ethylenebis(indenyl) dimethyl zirconium and phenol wascarried out in the same manner as in Example 93 except that phenol wasused instead of 2-trifluoromethylphenol. A catalyst component ofcolorless oil was obtained.

(2) Polymerization

The copolymerization of ethylene and 2-norbornene was carried out in thesame manner as in Example 160 except that 5 ml of toluene solutioncontaining 1.0 μmol of the catalyst component (r)-6 was used instead ofthe catalyst component (d)-3. The results are shown in Table 31.

TABLE 31 activity contents of Catalyst polymer yield (kg polymer/2-norbornene Example No. component (g) gZr) (mol %) Example 161 (f)-11.50 16.5 16.9 Example 162 (f)-2 2.27 24.9 18.6 Example 163 (f)-3 2.4727.1 20.7 Comparative Example 6 (r)-6 0.81 8.9 11.4

EXAMPLE 164 Copolymerization of Ethylene and Dicyclopentadiene

The polymerization was carried out under the same condition as inExample 160 except that 90 ml of toluene and 4.1 ml of dicyclopentadiene(30 mmol) were added to an autoclave. The yield amount of polymer was3.01 g and the activity per unit zirconium was 33.0 kg polymer/g Zr. Thecontent of dicyclopentadiene in the polymer was 24.1 mol %.

III. Durability Test of Catalyst EXAMPLE 165 (1) Preparation of CatalystComponent Solution

The procedure for the preparation of catalyst component solution wascarried out in an air atmosphere. 70 mg of the catalyst component (a)-7was put into a 50 ml conical flask and dissolved in 50 ml of toluene.Then, 5 ml of the solution of the catalyst component was taken out anddiluted with toluene up to 25 ml of total volume to obtain 0.5 μmol/l ofcatalyst concentration.

(2) Polymerization Test

The polymerization of ethylene was carried out in the same manner as inExample 96 by using the solution of catalyst component just after thepreparation thereof and after stirring with a magnetic stirrer for 24hours, respectively. The results of polymerization are shown in Table32.

COMPARATIVE EXAMPLE 7

The solution containing 0.5 μmol/l of dicyclopentadienyl dimethylzirconium instead of the catalyst component (a)-7 was prepared in thesame manner as in Example 165 and the polymerization was carried outwith the solution in the same manner as in Example 165. The results areshown in Table 32. The degree of reduction of activity was very largewhen the solution of catalyst component stirred for 24 hours was used inthe case of comparative are shown in Table 32. The degree of reductionof activity was very large when the solution of catalyst componentstirred for 24 hours was used in the case of comparative example 7,whereas the degree of the reduction was very small when the solution ofcatalyst component stirred for 24 hours was used in the case of example165.

TABLE 32 Treatment of the solution Catalyst activity of catalyst Usagepolymer yield (kg polymer/ Example No. component (μmol) (g) g Zr)Example 165 immediately 0.05 13.9 3030 after dilution after 0.05 13.32900 stirring for 24 hours Comparative immediately 0.05 11.3 2460Example 7 after dilution after 0.05 6.5 1420 stirring for 24 hours

According to the present invention, the transition metal compound ascatalyst component for the polymerization of olefins, does not contain ahalogen bound directly to the metal so that hydrogen halide causingcorrosion is not generated by hydrolysis, of the transition metalcompound, and has a high stability to oxygen and moisture so that it maybe easily handled and stored in good stability. Further, the catalystcontaining the transition, metal compound according to the presentinvention shows an excellent activity for the homo- and copolymerizationof olefins.

What is claimed is:
 1. A catalyst for the polymerization of olefinscomprising: [A] a catalyst component comprising a transition metalcompound represented by the general formula [1] or [2]: (R_(a)Cp)_(m)(R′_(b) Cp)_(n)M(—X—Ar—Y_(c))_(4−(m+n))  [1] wherein M representstitanium, zirconium or hafnium, Cp represents a radical having thecyclopentadienyl skeleton, R and R′ each represents a hydrogen atom, analkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilylradical, X represents an oxygen or a sulphur atom, Ar represents anaromatic ring, Y represents a hydrogen atom, a hydrocarbon radical, asilyl radical, a halogen atom, a halogenated hydrocarbon radical, anitrogen-containing organic radical, an oxygen-containing organicradical or a sulphur-containing organic radical, each of a and b is aninteger of 0 to 5, each of m and n is an integer of 0 to 3 and m+n is aninteger of 1 to 3, and c is an integer of 1 to 5, with a proviso that Yis not a hydrogen atom when Ar is a benzene ring; R″(F_(d) Cp) (R′_(e)Cp)M(—X—Ar—Y_(c))₂  [2] wherein M represents titanium, zirconium orhafnium, Cp represents a radical having the cyclopentadienyl skeleton, Rand R′ each represents a hydrogen atom, an alkyl, an alkenyl, an aryl,an alkylaryl, an arylalkyl or an alkylsilyl radical, R″ represents adivalent radical which links (R_(d) Cp) and (R′_(e) Cp) and is selectedfrom the group consisting of an alkylene, an arylalkylene, adialkylsilylene, a dialkylgermylene, an alkylphosphindiyl or analkylimino radical, X represents an oxygen or a sulphur atom, Arrepresents an aromatic ring, Y represents a hydrogen atom, a hydrocarbonradical, a silyl radical, a halogen atom, a halogenated hydrocarbonradical, a nitrogen-containing organic radical, an oxygen-containingorganic radical or a sulphur-containing organic radical, each of d and eis an integer of 0 to 4, and c is an integer of 1 to 5, with a provisothat Y is not a hydrogen atom when Ar is a benzene ring; and [B] anorganic aluminum oxy compound or a cation generator.
 2. A catalyst forthe polymerization of olefins according to the claim 1, wherein Arrepresents a benzene or naphthalene ring in the general formula [1] and[2].
 3. A catalyst for the polymerization of olefins according to claim1, wherein Y is a substituent selected from the group consisting of ahydrogen atom, an alkyl radical having 1 to 10 carbon atoms, an arylradical having 6 to 10 carbon atoms, an alkenyl radical having 2 to 10carbon atoms, an alkynyl radical having 2 to 10 carbon atoms, anarylalkyl radical having 7 to 20 carbon atoms, an arylalkenyl radicalhaving 8 to 20 carbon atoms, an alkylaryl radical having 7 to 20 carbonatoms; a silyl radical; a halogen atom, a halogenated hydrocarbonradical; cyano, nitro, nitroso, isocyanide, cyanate, isocyanate, amino,amido; alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy;alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl andarylsulfonyl radical.
 4. A catalyst for the polymerization of olefinsaccording to claim 1, said catalyst further comprising: an organicaluminum compound.
 5. A catalyst for the polymerization of olefinsaccording to claim 2, wherein Y is a substituent selected from the groupconsisting of a hydrogen atom, an alkyl radical having 1 to 10 carbonatoms, an aryl radical having 6 to 10 carbon atoms, an alkenyl radicalhaving 2 to 10 carbon atoms, an alkynyl radical having 2 to 10 carbonatoms, an arylalkyl radical having 7 to 20 carbon atoms, an arylalkenylradical having 8 to 20 carbon atoms, an alkylaryl radical having 7 to 20carbon atoms; a silyl radical; a halogen atom, a halogenated hydrocarbonradical; cyano, nitro, nitroso, isocyanide, cyanate, isocyanate, amino,amido; alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy;alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl andarylsulfonyl radical.
 6. A catalyst for the polymerization of olefinsaccording to claim 2, said catalyst further comprising: an organicaluminum compound.
 7. A catalyst for the polymerization of olefinsaccording to claim 3, said catalyst further comprising: an organicaluminum compound.
 8. A catalyst for the polymerization of olefinsaccording to claim 5, said catalyst flitter comprising: an organicaluminum compound.